Method for producing organic thin film

ABSTRACT

An object of the present invention is to provide a method for producing an organic thin film, which enables rapid film formation, and enables a dense organic thin film with minimal impurities to be formed stably, and in a plurality of consecutive repetitions. 
     The present invention provides a method for producing an organic thin film in which an organic thin film is formed on the surface of a substrate, including a step (A) of bringing the substrate into contact with an organic solvent solution containing a metal-based surfactant having at least one hydrolysable group, and a catalyst capable of interacting with the metal-based surfactant, wherein the water contact within the organic solvent solution is either set or maintained within a predetermined range.

CROSS-REFERENCE TO PRIOR APPLICATION

This is a divisional of application Ser. No. 10/553,109 filed Mar. 13,2006, which is a National Stage Application of PCT/JP2004/05285 filedApr. 14, 2004, and claims the benefit of Japanese Patent ApplicationNos. 2003-109835, 2003-109719, 2003-321893, 2003-323173, 2004-058778,and 2004-108732 filed Apr. 15, 2003, Apr. 15, 2003, Sep. 12, 2003, Sep.16, 2003, Mar. 3, 2004, and Apr. 1, 2004. The entire disclosure of theprior applications are hereby incorporated by reference herein in itsentirety.

TECHNICAL FIELD

The present invention relates to a method for producing an organic thinfilm that is formed on the surface of a substrate via metal-oxygenbonds, an organic thin film forming solution used in the method, and anorganic thin film produced using the method.

BACKGROUND ART

A number of methods for producing chemically adsorbed films that exhibitexcellent resistance to peeling, a high level of transparency, and donot impair the gloss of the substrate surface or the substratetransparency are already known as suitable methods for forming a coatingfilm that improves the properties of a substrate surface (see JapaneseUnexamined Patent Application, First Publication No. Hei 4-132637,Japanese Unexamined Patent Application, First Publication No. Hei4-221630, and Japanese Unexamined Patent Application, First PublicationNo. Hei 4-367721).

As a method for forming a chemically adsorbed film on a substratesurface that contains active hydrogen, a method is known in which amixed solution containing at least an alkoxysilane-based surfactant, anon-aqueous solvent with no active hydrogen, and at least one silanolcondensation catalyst selected from a group consisting of carboxylicacid metal salts, carboxylate metal salts, carboxylic acid metal saltpolymers, carboxylic acid metal salt chelates, titanate esters, andtitanate ester chelates is brought into contact with a substratesurface, thereby forming a chemically adsorbed film that is covalentlybonded to the substrate surface via siloxane bonds (see JapaneseUnexamined Patent Application, First Publication No. Hei 8-337654).

As a method for forming a chemically adsorbed film that exhibitscrystallinity on a substrate surface, a method is known in which anorganic solvent solution of a silane-based surfactant is developed onthe surface of a silicon wafer onto which purified water has beendripped, thereby forming a crystalline monomolecular film (see Bull.Chem. Soc. Jpn., 74, 1397 to 1401 (2001)).

Methods for forming water repellent films are also known in which, byusing the monomer or polymer of a hydrolysis product of a fluoroalkylgroup-containing silane compound, produced by hydrolysis in the presenceof an acid catalyst, a water repellent film formed from a monomolecularlayer of the hydrolysis product is fixed to the substrate surface viasilanol groups (see Japanese Unexamined Patent Application, FirstPublication No. Hei 11-228942, Japanese Unexamined Patent Application,First Publication No. Hei 11-322368).

As a method for forming a monomolecular film on a substrate surface thatcontains active hydrogen, a method for producing a chemically adsorbedmonomolecular film is known which includes the steps of coating thesurface of a substrate, in a dry atmosphere, with a chemical adsorptionsolution prepared using a non-aqueous organic solvent and a silane-basedsurfactant, chemically reacting the surfactant molecules within theadsorption solution with the surface of the substrate while the organicsolvent is concentrated by evaporation, thereby bonding and fixing oneend of the surfactant molecules to the substrate surface, and then usingan organic solvent to wash and remove any unreacted surfactant left onthe substrate surface following evaporation of the organic solvent (seeJapanese Unexamined Patent Application, First Publication No. Hei11-147074).

However, a number of problems arise in all of the methods describedabove, including the lengthy time required to form the film, the factthat residual silanol condensation catalyst remains in the film,inhibiting the chemical adsorption and preventing formation of a densemonomolecular film, the fact that acidic materials are generated,meaning there are restrictions on the type of substrate that can beused, and the fact that film formation must be conducted in anon-aqueous system. The stable provision of dense monomolecular filmswith minimal impurities is keenly sought, particularly formicropatterning in the design of electronic devices and the like.Furthermore, using the conventional methods described above, no examplesare known of the formation of a crystalline chemically adsorbed film onthe surface of an amorphous substrate.

DISCLOSURE OF INVENTION

The present invention takes the above circumstances associated with theconventional technology into consideration, with an object of providinga method for producing an organic thin film which enables rapid filmformation, and enables a dense organic thin film with minimal impuritiesto be formed stably, and in a plurality of consecutive repetitions.

As a result of intensive investigation aimed at achieving the aboveobject, the inventors of the present invention discovered that bybringing a substrate into contact with either an organic solventsolution containing a metal-based surfactant having at least onehydrolyzable group and a catalyst capable of interacting with themetal-based surfactant, wherein the water content within the solution iseither set or maintained within a predetermined range, or an organicsolvent solution containing a metal-based surfactant having at least onehydroxyl group, wherein the water content within the solution is eitherset or maintained within a predetermined range, homogenous organic thinfilms could be formed stably and rapidly by two or more repetitions ofthe film formation process using the same solution.

In other words, the present invention includes the following aspects.

(1) A method for producing an organic thin film in which an organic thinfilm is formed on the surface of a substrate, including a step (A) ofbringing the substrate into contact with an organic solvent solutioncontaining a metal-based surfactant having at least one hydrolyzablegroup, and a catalyst capable of interacting with the metal-basedsurfactant, wherein the water content within the organic solventsolution is either set or maintained within a predetermined range(2) A method for producing an organic thin film according to the aspect(1) above, wherein the organic solvent solution is prepared by usingfrom 0.001 to 1 mol, or an oxide-equivalent quantity of 0.001 to 1 mol,of the catalyst capable of interacting with the metal-based surfactantper 1 mol of the metal-based surfactant.(3) A method for producing an organic thin film in which an organic thinfilm is formed on the surface of a substrate, including a step (A) ofbringing the substrate into contact with an organic solvent solutioncontaining a metal-based surfactant having at least one hydrolyzablegroup, and a catalyst capable of interacting with the metal-basedsurfactant, wherein the water content within the organic solventsolution is maintained within a predetermined range, and the step (A) isrepeated at least two times using the same solution.(4) A method for producing an organic thin film according to the aspect(3) above, wherein in repeating the step (A) two or more times, the step(A) is conducted with two or more substrates using the same solution.(5) A method for producing an organic thin film according to any one ofaspects (1) to (4) above, further including a step (B) of washing thesubstrate following the step (A).(6) A method for producing an organic thin film according to any one ofthe aspects (1) to (5) above, further including a step (C) of heatingthe substrate following the step (A).(7) A method for producing an organic thin film according to aspect (6)above, further including a step (B) of washing the substrate followingthe step (A), but prior to the step (C).(8) A method for producing an organic thin film according to any one ofthe aspects (1) to (7) above, wherein by providing a water layer thatcontacts the organic solvent solution, the water content within theorganic solvent solution is either set or maintained within apredetermined range,(9) A method for producing an organic thin film according to any one ofthe aspects (1) to (8) above, wherein by incorporating a water-retentivematerial in a hydrated state within the organic solvent solution, thewater content within the organic solvent solution is either set ormaintained within a predetermined range.(10) A method for producing an organic thin film according to the aspect(9) above, wherein the water-retentive material is a glass fiber filter.(11) A method for producing an organic thin film according to any one ofthe aspects (1) to (10) above, wherein by blowing a gas containingmoisture through the organic solvent solution, the water content withinthe organic solvent solution is either set or maintained within apredetermined range.(12) A method for producing an organic thin film according to any one ofthe aspects (1) to (11) above, wherein the water content within theorganic solvent solution is either set or maintained within a range from50 to 1,000 ppm.(13) A method for producing an organic thin film according to any one ofthe aspects (1) to (12) above, wherein the water content within thepredetermined range is the measured value, obtained by a Karl Fischermethod, for a solution aliquot sampled from the organic solventsolution.(14) A method for producing an organic thin film according to any one ofthe aspects (1) to (13) above, wherein the catalyst capable ofinteracting with the metal-based surfactant is at least one materialselected from a group consisting of metal oxides; metal hydroxides;metal alkoxides; chelated or coordinated metal compounds; partialhydrolysis products of metal alkoxides; hydrolysis products obtained bytreating a metal alkoxide with a two-fold or greater equivalence ofwater; organic acids; silanol condensation catalysts; and acidcatalysts.(15) A method for producing an organic thin film according to the aspect(14) above, wherein a compound with a pKa value within a range from 1 to6 is used as the organic acid.(16) A method for producing an organic thin film according to the aspect(14) above, wherein the partial hydrolysis product of a metal alkoxideis able to be stably dispersed in an organic solvent withoutaggregating, even in the absence of acids, bases, and/or dispersionstabilizers.(17) A method for producing an organic thin film according to either theaspect (14) or the aspect (16), wherein the partial hydrolysis productof a metal alkoxide is a product obtained by hydrolyzing the metalalkoxide in an organic solvent, using from 0.5 to less than 2.0 mols ofwater per 1 mol of the metal alkoxide, at a temperature within a rangefrom −100° C. to the reflux temperature of the organic solvent.(18) A method for producing an organic thin film according to any one ofthe aspects (14) to (17) above, wherein the metal within the metaloxide; metal hydroxide; metal alkoxide; chelated or coordinated metalcompound; partial hydrolysis product of a metal alkoxide; or hydrolysisproduct obtained by treating a metal alkoxide with a two-fold or greaterequivalence of water is one or more metals selected from a groupconsisting of titanium, zirconium, aluminum, silicon, germanium, indium,tin, tantalum, zinc, tungsten, and lead.(19) A method for producing an organic thin film according to any one ofthe aspects (1) to (18) above, wherein the metal-based surfactant havingat least one hydrolyzable group is a compound represented by a formula(I) shown below:

R¹ _(n)MX_(m−n)  (I)

(wherein, R¹ represents a hydrocarbon group that may contain asubstituent, a halogenated hydrocarbon group that may contain asubstituent, a hydrocarbon group containing a linkage group, or ahalogenated hydrocarbon group containing a linkage group, M representsat least one metal atom selected from a group consisting of a siliconatom, germanium atom, tin atom, titanium atom, and zirconium atom, Xrepresents a hydroxyl group or a hydrolyzable group, n represents aninteger from 1 to (m−1), m represents the atomic valence of the metal M,and in those cases where n is 2 or greater, the X groups may be the sameor different, and in those cases where (m−n) is 2 or greater, the Xgroups may be the same or different, although of the (m−n) X groups, atleast one X group must be a hydrolyzable group).(20) A method for producing an organic thin film according to any one ofthe aspects (1) to (18) above, wherein the metal-based surfactant havingat least one hydrolyzable group is a compound represented by a formula(II) shown below:

R² ₃C—(CR³ ₂)_(p)—R⁴ _(q)-MY_(r)X_(m−r−1)  (II)

(wherein, M represents at least one metal atom selected from a groupconsisting of a silicon atom, germanium atom, tin atom, titanium atom,and zirconium atom, X represents a hydroxyl group or a hydrolyzablegroup, R² and R³ each represent, independently, a hydrogen atom or afluorine atom, R⁴ represents an alkylene group, vinylene group,ethynylene group, arylene group, or a bivalent linkage group thatcontains a silicon atom and/or an oxygen atom, Y represents a hydrogenatom, or an alkyl group, alkoxy group, fluorine-containing alkyl group,or fluorine-containing alkoxy group, p represents either 0 or a naturalnumber, q represents either 0 or 1, r represents an integer from 0 to(m−2), and in those cases where r is 2 or greater, the Y groups may bethe same or different, and in those cases where (m−r−1) is 2 or greater,the X groups may be the same or different, although of the (m−r−1) Xgroups, at least one X group must be a hydrolyzable group).(21) A method for producing an organic thin film according to any one ofthe aspects (1) to (20) above, wherein the hydrolyzable group of thegroup X is a halogen atom, an alkoxy group of C1 to C6, or an acyloxygroup.(22) A method for producing an organic thin film in which an organicthin film is formed on the surface of a substrate, including a step ofbringing the substrate into contact with an organic solvent solutioncontaining a metal-based surfactant having at least one hydroxyl group,wherein the water content within the organic solvent solution is eitherset or maintained within a predetermined range.(23) A method for producing an organic thin film according to the aspect(22) above, wherein the water content within the organic solventsolution is either set or maintained within a range from 50 to 1,000ppm.(24) A method for producing an organic thin film according to either theaspect (22) or the aspect (23), wherein the metal-based surfactanthaving at least one hydroxyl group is a compound represented by aformula (III) shown below:

R¹ _(n)MX_(m−n−1)(OH)  (III)

(wherein, R¹ represents a hydrocarbon group that may contain asubstituent, a halogenated hydrocarbon group that may contain asubstituent, a hydrocarbon group containing a linkage group, or ahalogenated hydrocarbon group containing a linkage group, M representsat least one metal atom selected from a group consisting of a siliconatom, germanium atom, tin atom, titanium atom, and zirconium atom, Xrepresents a hydroxyl group or a hydrolyzable group, n represents aninteger from 1 to (m−1), m represents the atomic valence of the metal M,and in those cases where n is 2 or greater, the R¹ groups may be thesame or different, and in those cases where (m−n−1) is 2 or greater, theX groups may be the same or different).(25) A method for producing an organic thin film according to any one ofthe aspects (1) to (24) above, wherein the step of bringing thesubstrate into contact with the organic solvent solution is conductedwithin a space that is maintained at a humidity of at least 40% RH.(26) A method for producing an organic thin film according to any one ofthe aspects (1) to (24) above, wherein the step of bringing thesubstrate into contact with the organic solvent solution is conductedwithin a space that is maintained at a humidity of at least 60% RH.(27) A method for producing an organic thin film according to any one ofthe aspects (1) to (26) above, wherein the organic solvent solution is ahydrocarbon-based solvent solution or a fluorinated hydrocarbon-basedsolvent solution.(28) A method for producing an organic thin film according to any one ofthe aspects (1) to (27) above, wherein the organic thin film is acrystalline organic thin film.(29) A method for producing an organic thin film according to any one ofthe aspects (1) to (28) above, wherein the organic thin film is amonomolecular film.(30) A method for producing an organic thin film according to any one ofthe aspects (1) to (29) above, wherein a substrate containing activehydrogen at the surface is used as the substrate.(31) A method for producing an organic thin film according to any one ofthe aspects (1) to (30) above, wherein the substrate is formed from atleast one material selected from a group consisting of glass, siliconwafers, ceramics, metals, and plastics.(32) A method for producing an organic thin film according to any one ofthe aspects (1) to (31) above, wherein the organic thin film is achemically adsorbed film.(33) A method for producing an organic thin film according to any one ofthe aspects (1) to (32) above, wherein the organic thin film is aself-assembly film.

Furthermore, as a result of discovering that in the aforementionedorganic solvent solution, the metal-based surfactant having at least onehydrolyzable group or the metal-based surfactant having at least onehydroxyl group forms an aggregate (aspect 34), the following aspects ofthe present invention were also identified.

(35) A self-assembly film forming solution for forming a self-assemblyfilm on the surface of a substrate, wherein the molecules for formingthe self-assembly film form an aggregate within the solution.(36) A self-assembly film forming solution according to the aspect (35),wherein the molecules for forming the self-assembly film are moleculesof either a metal-based surfactant having at least one hydroxyl group orhydrolyzable group, or a derivative thereof(37) A self-assembly film forming solution according to either theaspect (35) or the aspect (36), wherein the aggregate is obtained bytreating a metal-based surfactant having at least one hydroxyl group orhydrolyzable group with a catalyst capable of interacting with themetal-based surfactant, and water.(38) A self-assembly film forming solution according to any one of theaspects (35) to (37), wherein the metal-based surfactant having at leastone hydroxyl group or hydrolyzable group is a compound represented by aformula (IV) shown below:

R¹¹ _(n1)M¹X¹ _(m1−n1)  (IV)

(wherein, R¹¹ represents a hydrocarbon group that may contain asubstituent, a halogenated hydrocarbon group that may contain asubstituent, a hydrocarbon group containing a linkage group, or ahalogenated hydrocarbon group containing a linkage group, M¹ representsat least one metal atom selected from a group consisting of a siliconatom, germanium atom, tin atom, titanium atom, and zirconium atom, X¹represents a hydroxyl group or a hydrolyzable group, n₁ represents aninteger from 1 to (m₁−1), m₁ represents the atomic valence of the metalM¹, and in those cases where n₁ is 2 or greater, the R¹¹ groups may bethe same or different, and in those eases where (m₁−n₁) is 2 or greater,the X¹ groups may be the same or different).(39) A self-assembly film forming solution according to any one of theaspects (35) to (37), wherein the metal-based surfactant having at leastone hydroxyl group or hydrolyzable group is a compound represented by aformula (V) shown below:

R²¹ ₃C—(CR³¹ ₂)_(p1)—R⁴¹ _(q1)-M²Y² _(r2)X² _(m2−r2−1)  (V)

(wherein, M² represents at least one metal atom selected from a groupconsisting of a silicon atom, germanium atom, tin atom, titanium atom,and zirconium atom, X² represents a hydroxyl group or a hydrolyzablegroup, R²¹ and R³¹ each represent, independently, a hydrogen atom or afluorine atom, R⁴¹ represents an alkylene group, vinylene group,ethynylene group, arylene group, or a bivalent linkage group thatcontains a silicon atom and/or an oxygen atom, Y² represents a hydrogenatom, or an alkyl group, alkoxy group, fluorine-containing alkyl group,or fluorine-containing alkoxy group, p₁ represents either 0 or a naturalnumber, q₁ represents either 0 or 1, r₂ represents an integer from 0 to(m₂−2), and in those cases where r₂ is 2 or greater, the Y² groups maybe the same or different, and in those cases where (m₂−r₂−1) is 2 orgreater, the X² groups may be the same or different).(40) A self-assembly film forming solution according to any one of theaspects (35) to (39), wherein the hydrolyzable group is a halogen atom,an alkoxy group of C1 to C6, or an acyloxy group.(41) A self-assembly film forming solution according to any one of theaspects (35) to (40), wherein an average particle diameter of theaggregate is within a range from 10 to 1,000 nm.(42) A self-assembly film forming solution according to any one of theaspects (35) to (41), wherein the zeta potential of the aggregate isequal to or greater than the zeta potential of the substrate within thesame solution.

Furthermore, as a result of discovering that even if the substrate usedin the method for producing an organic thin film is not crystalline, theformed organic thin film exhibits crystallinity (aspect 43), thefollowing aspects of the present invention were also identified.

(44) A chemically adsorbed film formed on a substrate, wherein thesubstrate is not crystalline, and the chemically adsorbed film iscrystalline.(45) A chemically adsorbed film according to the aspect (44), which isformed using a metal-based surfactant having at least one hydroxyl groupor hydrolyzable group.(46) A chemically adsorbed film according to either the aspect (44) orthe aspect (45), wherein the chemically adsorbed film is a monomolecularfilm.(47) A chemically adsorbed film according to any one of the aspects (44)to (46), wherein the chemically adsorbed film is a self-assembly film.

Furthermore, as a result of discovering that in the method for producingan organic thin film, even if the step for bringing the organic solventsolution into contact with the substrate is a step in which at least onemethod selected from a group consisting of dipping methods, spin coatingmethods, roll coating methods, Meyer bar methods, screen printingmethods, offset printing methods, brush coating methods, and spraymethods is used to apply the organic solvent solution to the surface ofthe substrate, a monomolecular film can still be produced (aspect 48),the following aspects of the present invention were also identified.

(49) A method for producing a monomolecular film, including a step ofapplying an organic solvent solution containing a metal-based surfactanthaving a hydroxyl group, hydrocarbonoxy group, or acyloxy group to thesurface of a substrate, using at least one method selected from a groupconsisting of dipping methods, spin coating methods, roll coatingmethods, Meyer bar methods, screen printing methods, offset printingmethods, brush coating methods, and spray methods.(50) A method for producing a monomolecular film, wherein an organicsolvent solution containing a metal-based surfactant having a hydroxylgroup, hydrocarbonoxy group, or acyloxy group is dripped onto asubstrate, and pressure is then applied from above the dripped solutionto spread the solution across the substrate.(51) A method for producing a monomolecular film according to the aspect(50), wherein the method for applying pressure from above the drippedsolution is a method in which a film, a sheet, or a flat plate is laidon top of the substrate surface and rolled.(52) A method for producing a monomolecular film according to any one ofthe aspects (49) to (51), wherein a step of washing the substrate isprovided following the application step.(53) A method for producing a monomolecular film according to any one ofthe aspects (49) to (52), wherein a step of heating the substrate isprovided following the application step.(54) A method for producing a monomolecular film according to any one ofthe aspects (49) to (53), wherein the organic solvent solutioncontaining the metal-based surfactant also contains a catalyst capableof interacting with the metal-based surfactant.

As follows is a more detailed description of the present invention.

1) Method for Producing Organic Thin Film

A method for producing an organic thin film according to the presentinvention includes a step of bringing a substrate into contact witheither (a) an organic solvent solution containing a metal-basedsurfactant having at least one hydrolyzable group, and a catalystcapable of interacting with the metal-based surfactant (hereafter alsoreferred to as the “solution (a)”), or (b) an organic solvent solutioncontaining a metal-based surfactant having at least one hydroxyl group(hereafter also referred to as the “solution (b)”), wherein the watercontent within the organic solvent solution is either set or maintainedwithin a predetermined range.

There are no particular restrictions on the metal-based surfactanthaving at least one hydrolyzable group that is used within the solution(a) of the present invention, provided the surfactant contains at leastone hydrolyzable functional group and a hydrophobic group within thesame molecule, although the surfactant preferably contains ahydrolyzable group that is capable of reacting with an active hydrogenon the substrate surface to form a bond. Examples of other functionalgroups capable of reacting with an active hydrogen to form a bondinclude hydroxyl groups, and the surfactant may also comprise a hydroxylgroup. Specific examples of this type of metal-based surfactant includethe compounds represented by the aforementioned formula (I).

In the formula (I), the group R¹ represents a hydrocarbon group that maycontain a substituent, a halogenated hydrocarbon group that may containa substituent, a hydrocarbon group containing a linkage group, or ahalogenated hydrocarbon group containing a linkage group.

Examples of the hydrocarbon group within the hydrocarbon group that maycontain a substituent include alkyl groups of 1 to 30 carbon atoms suchas a methyl group, ethyl group, n-propyl group, isopropyl group, n-butylgroup, isobutyl group, sec-butyl group, t-butyl group, n-pentyl group,isopentyl group, neopentyl group, t-pentyl group, n-hexyl group,isohexyl group, n-heptyl group, n-octyl group, or n-decyl group; alkenylgroups of 2 to 30 carbon atoms, such as a vinyl group, propenyl group,butenyl group, or pentenyl group; and aryl groups such as a phenyl groupor naphthyl group.

Examples of the halogenated hydrocarbon group within the aforementionedhalogenated hydrocarbon group that may contain a substituent includehalogenated alkyl groups of 1 to 30 carbon atoms, halogenated alkenylgroups of 2 to 30 carbon atoms, and halogenated aryl groups. Examples ofthe halogen atom include a fluorine atom, chlorine atom, or bromineatom, although a fluorine atom is preferred. Specific examples includegroups in which one or more hydrogen atoms from the hydrocarbon groupslisted above have been substituted with a halogen atom such as afluorine atom, chlorine atom, or bromine atom.

Of these groups, halogenated hydrocarbon groups in which two or morehydrogen atoms from an alkyl group of 1 to 30 carbon atoms have beensubstituted with halogen atoms are preferred, and fluorinated alkylgroups in which two or more hydrogen atoms from an alkyl group of 1 to30 carbon atoms have been substituted with fluorine atoms areparticularly desirable. Furthermore, in those cases where thefluorinated alkyl group has a branched structure, the branched portionsare preferably short chains of 1 to 4 carbon atoms, and even morepreferably 1 to 2 carbon atoms.

Amongst fluorinated alkyl groups, groups in which one or more fluorineatoms are bonded to a terminal carbon atom are preferred, and groupswith a —CF₃ grouping in which three fluorine atoms are bonded to aterminal carbon atom are particularly desirable, although groups inwhich the terminals are not substituted with fluorine atoms, butnon-terminal carbon atoms within the molecular chain are substitutedwith a fluorine atom are also suitable. Groups which contain, at aterminal position, a pefluoroalkyl portion in which all of the hydrogenatoms of an alkyl group have been substituted with fluorine atoms, andwhich contain an alkylene group represented by the formula —(CH₂)_(h)—(wherein, h represents an integer from 1 to 6, and preferably an integerfrom 2 to 4) between the metal atoms M described below are particularlydesirable.

The number of fluorine atoms within the fluorinated alkyl group, whenrepresented by the formula [(number of fluorine atoms within thefluorinated alkyl group)/(number of hydrogen atoms within the equivalentalkyl group with the same number of carbon atoms)×100]%, is preferablyat least 60%, and even more preferably 80% or higher.

Examples of the substituent within the hydrocarbon group that maycontain a substituent or the halogenated hydrocarbon group that maycontain a substituent include a carboxyl group, amide group, imidegroup, ester group, an alkoxy group such as a methoxy group or ethoxygroup, or a hydroxyl group. The number of these substituents ispreferably within a range from 0 to 3.

Examples of the hydrocarbon group within the aforementioned hydrocarbongroup containing a linkage group include the same groups listed above asthe hydrocarbon group within the hydrocarbon group that may contain asubstituent.

Furthermore, examples of the halogenated hydrocarbon group within theaforementioned halogenated hydrocarbon group containing a linkage groupinclude the same groups listed above as the halogenated hydrocarbongroup within the halogenated hydrocarbon group that may contain asubstituent.

The linkage group preferably exists either between a carbon-carbon bondof the hydrocarbon group or halogenated hydrocarbon group, or between acarbon atom of the hydrocarbon group and the metal atom M describedbelow.

Specific examples of this linkage group include —O—, —S—, —SO₂—, —CO—,—C(═O)O—, and —C(═O)NR⁵¹ (wherein, R⁵¹ represents a hydrogen atom, or analkyl group such as a methyl group, ethyl group, n-propyl group, orisopropyl group).

Of the above possibilities, from the viewpoints of water repellency anddurability, the R¹ group is preferably an alkyl group of 1 to 30 carbonatoms, a fluorinated alkyl group of 1 to 30 carbon atoms, or afluorinated alkyl group containing a linkage group.

Specific examples of the R¹ group include CH₃—, CH₃CH₂—, (CH₃)₂CH—,(CH₃)₃C—, CH₃(CH₂)₂—, CH₃(CH₂)₃—, CH₃(CH₂)₄—, CH₃(CH₂)₅—, CH₃(CH₂)₆—,CH₃(CH₂)₇—, CH₃(CH₂)₈—, CH₃(CH₂)₉—, CH₃(CH₂)_(m)—, CH₃(CH₂)₁₁—,CH₃(CH₂)₁₂—, CH₃(CH₂)₁₃—, CH₃(CH₂)₁₄—, CH₃(CH₂)₁₅—, CH₃(CH₂)₁₆—,CH₃(CH₂)₁₇—, CH₃(CH₂)₁₈—, CH₃(CH₂)₁₉—, CH₃(CH₂)₂₀—, CH₃(CH₂)₂₁—,CH₃(CH₂)₂₂—, CH₃(CH₂)₂₃—, CH₃(CH₂)₂₄—, and CH₃(CH₂)₂₅—, CF₃—, CF₃CF₂—,(CF₃)₂CF—, (CF₃)₃C—, CF₃(CH₂)₂—, CF₃(CF₂)₃(CH₂)₂—, CF₃(CF₂)₅(CH₂)₂—,CF₃(CF₂)₇(CH₂)₂—, CF₃(CF₂)₃(CH₂)₃—, CF₃(CF₂)₅(CH₂)₃—, CF₃(CF₂)₇(CH₂)₃—,CF₃(CF₂)₄O(CF₂)₂(CH₂)₂—, CF₃(CF₂)₄O(CF₂)₂(CH₂)₃—,CF₃(CF₂)₇O(CF₂)₂(CH₂)₂—, CF₃(CF₂)₇CONH(CH₂)₂—, CF₃(CF₂)₇CONH(CH₂)₃—, andCF₃(CF₂)₃O[CF(CF₃)CF(CF₃)O]₂CF(CF₃)CONH(CH₂)₃—,

CH₃(CF₂)₇(CH₂)₂—, CH₃(CF₂)₈(CH₂)₂—, CH₃(CF₂)₉(CH₂)₂—, CH₃(CF₂)₁₀(CH₂)₂—,CH₃(CF₂)₁₁(CH₂)₂—, CH₃(CF₂)₁₂(CH₂)₂—, CH₃(CF₂)₇(CH₂)₃—,CH₃(CF₂)₉(CH₂)₃—, CH₃(CF₂)₁₁(CH₂)₃—, CH₃CH₂(CF₂)₆(CH₂)₂—,CH₃CH₂(CF₂)₈(CH₂)₂—, CH₃CH₂(CF₂)₁₀(CH₂)₂—, CH₃(CF₂)₄O(CF₂)₂(CH₂)₂—,CH₃(CF₂)₇(CH₂)₂O(CH₂)₃—, CH₃(CF₂)₈(CH₂)₂O(CH₂)₃—,CH₃(CF₂)₉(CH₂)₂O(CH₂)₃—, CH₃CH₂(CF₂)₆(CH₂)₂O(CH₂)₃—,CH₃(CF₂)₆CONH(CH₂)₃—, CH₃(CF₂)₈CONH(CH₂)₃—, andCH₃(CF₂)₃O[CF(CF₃)CF(CF₃)O]₂CF(CF₃)CONH(CH₂)₃—, although the presentinvention is in no way restricted to the above groups.

M represents an atom selected from a group consisting of a silicon atom,germanium atom, tin atom, titanium atom, and zirconium atom. Of these,from the viewpoints of availability and reactivity, a silicon atom isparticularly preferred.

X represents a hydroxyl group or a hydrolyzable group, and there are noparticular restrictions on the hydrolyzable group, provided itdecomposes on reaction with water. Specific examples of the hydrolyzablegroup include alkoxy groups of 1 to 6 carbon atoms that may contain asubstituent, hydrocarbonoxy groups that may contain a substituent,acyloxy groups that may contain a substituent, halogen atoms such as afluorine atom, chlorine atom, bromine atom, or iodine atom, as well asan isocyanate group, cyano group, amino group, or amide group.

Of these, alkoxy groups of 1 to 6 carbon atoms; hydrocarbonoxy groupssuch as alicyclic and aromatic hydrocarbonoxy groups, alkenyloxy groups,and aralkyloxy groups; and acyloxy groups such as an acetoxy group; allof which may contain a substituent, are particularly preferred.

Specific examples of suitable alkoxy groups of 1 to 6 carbon atomsinclude a methoxy group, ethoxy group, n-propoxy group, isopropoxygroup, n-butoxy group, sec-butoxy group, t-butoxy group, n-pentyloxygroup, and n-hexyloxy group.

Specific examples of suitable acyloxy groups include an acetoxy group,propionyloxy group, propanoyloxy group, n-propylcarbonyloxy group,isopropylcarbonyloxy group, n-butylcarbonyloxy group, and propanoyloxygroup; examples of suitable alicyclic hydrocarbonoxy groups include acyclopropyloxy group, cyclopropylmethyloxy group, cyclohexyloxy group,and norbornyloxy group; examples of suitable alkenyloxy group include anallyloxy group, and a vinyloxy group; examples of suitable alkynyloxygroups include a propargyloxy group; examples of suitable aralkyloxygroups include benzyloxy group, and phenethyloxy group; examples ofsuitable aromatic hydrocarbonoxy groups include a phenoxy group and anaphthyloxy group; and a benzoyloxy group is also suitable.

Examples of the substituent within these groups include a carboxylgroup, amide group, imide group, ester group, or hydroxyl group. Ofthese possible groups, X is preferably a hydroxyl group, halogen atom,alkoxy group of 1 to 6 carbon atoms, acyloxy group, or isocyanate group,and an alkoxy group of 1 to 4 carbon atoms or an acyloxy group isparticularly desirable.

m represents the atomic valence of the metal atom M.

n represents an integer from 1 to (m−1). In order to enable productionof a high density organic thin film, n is preferably 1.

In those cases where n is 2 or greater, the R¹ groups may be either thesame or different.

Furthermore, in those cases where (m−n) is 2 or greater, the X groupsmay either be the same or different, although of the (m−n) X groups, atleast one X group must be a hydrolyzable group.

Of the compounds represented by the formula (I), those compoundsrepresented by the formula (II) represent preferred configurations.

In the formula (II), R⁴ represents an alkylene group, vinylene group,ethynylene group, arylene group, or a bivalent functional group thatcontains a silicon atom and/or an oxygen atom. Specific examples of theR⁴ group include the functional groups shown in the formulas below.

In the above formulas, a and b each represent an arbitrary naturalnumber of at least 1.

Y represents a hydrogen atom; an alkyl group such as a methyl group,ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutylgroup, sec-butyl group, t-butyl group, n-pentyl group, isopentyl group,neopentyl group, t-pentyl group, n-hexyl group, or isohexyl group; analkoxy group such as a methoxy group, ethoxy group, n-propoxy group,isopropoxy group, n-butoxy group, sec-butoxy group, t-butoxy group,n-pentyloxy group, or n-hexyloxy group; a fluorinated alkyl group inwhich a portion of, or all of, the hydrogen atoms of an alkyl group havebeen substituted with fluorine atoms; or a fluorinated alkoxy group inwhich a portion of, or all of, the hydrogen atoms of an alkoxy grouphave been substituted with fluorine atoms.

r represents either 0 or an integer from 1 to (m−2), although in orderto enable production of a high density adsorbed film, r is preferably 0.In those cases where r is 2 or greater, the Y groups may be the same ordifferent, and in those cases where (m−r−1) is 2 or greater, the Xgroups may be the same or different. However, of the (m−r−1) X groups,at least one X group must be a hydrolyzable group.

In addition to the compounds represented by the formula (II), otherpreferred configurations of the compounds represented by the formula (I)include those shown below.

CH₃—(CH₂)_(g)-MY_(r)X_(m−r−1)  (1)

CH₃—(CH₂)_(s)—O—(CH₂)_(t)-MY_(r)X_(m−r−1)  (2)

CH₃—(CH₂)_(u)—Si(CH₃)₂—(CH₂)_(v)MY_(r)X_(m−r−1)  (3)

CF₃COO—(CH₂)_(w)-MY_(r)X_(m−r−1)  (4)

In the above formulas, g, s, t, u, v, and w each represent an arbitraryinteger, and particularly preferred ranges for these values are from 1to 25 for g, from 0 to 12 for s, from 1 to 20 for t, from 0 to 12 for u,from 1 to 20 for v, and from 1 to 25 for w.

M, Y, X, r, and m have the same meanings as defined in relation to theformula (II).

Specific examples of compounds represented by the formula (I) includethose listed below.

In the following examples, compounds in which the metal atom M is asilicon atom are shown as representative examples, but the presentinvention is not limited to these cases. Furthermore, the hydrolyzablegroups are also not limited to the functional groups shown in theexamples, and compounds containing other hydrolyzable groups are alsopossible.

CH₃CH₂O(CH₂)₁₅Si(OCH₃)₃ CF₃CH₂O(CH₂)₁₅Si(OCH₃)₃CH₃(CH₂)₂Si(CH₃)₂(CH₂)₁₅SOCH₃)₃ CH₃(CH₂)₆Si(CH₃)₂(CH₂)₉Si(OCH₃)₃CH₃COO(CH₂)₁₅Si(OCH₃)₃ CF₃(CF₂)₅(CH₂)₂Si(OCH₃)₃CF₃(CF₂)₇—(CH═CH)₃—Si(OCH₃)₃ CH₃CF₂O(CH₂)₁₅Si(OC₂H₅)₃CH₃(CH₂)₂Si(CH₃)₂(CH₂)₁₅Si(OC₂H₅)₃ CH₃(CH₂)₆Si(CH₃)₂(CH₂)₉Si(OC₂H₅)₃CF₃(CH₂)₆Si(CH₃)₂(CH₂)₉Si(OC₂H₅)₃ CH₃COO(CH₂)₁₅Si(OC₂H₅)₃CF₃COO(CH₂)₁₅Si(OC₂H₅)₃ CF₃COO(CH₂)₁₅Si(OCH₃)₃ CF₃(CF₂)₉(CH₂)₂Si(OC₂H₅)₃CF₃(CF₂)₇—(CH₂)₂Si(OC₂H₅)₃ CF₃(CF₂)₅(CH₂)₂Si(OC₂H₅)₃CF₃(CF₂)₇(CH═CH)₃Si(OC₂H₅)₃ CF₃(CF₂)₉(CH₂)₂Si(CH₃)₃CF₃(CF₂)₅(CH₂)₂Si(OCH₃)₃ CF₃(CF₂)₇(CH₂)₂Si(CH₃)(OC₂H₅)₂CF₃(CF₂)₇(CH₂)₂Si(CH₃)(OCH₃)₂ CF₃(CF₂)₇(CH₂)₂Si(CH₃)₂(OC₂H₅)CF₃(CF₂)₇(CH₂)₂Si(CH₃)₂(OCH₃) CF₃(CH₂)₂Si(OCH₃)₃CF₃(CF₂)₃(CH₂)₂Si(OCH₃)₃ CF₃(CF₂)₅(CH₂)₂Si(OCH₃)₃ CF₃(CF₂)₇(CH₂)₂SOCH₃)₃CF₃(CF₂)₃(CH₂)₃Si(OCH₃)₃ CF₃(CF₂)₅(CH₂)₃Si(OCH₃)₃CF₃(CF₂)₇(CH₂)₃Si(OCH₃)₃ CF₃(CF₂)₄O(CF₂)₂(CH₂)₂Si(OCH₃)₃CF₃(CF₂)₄O(CF₂)₂(CH₂)₃Si(OCH₃)₃ CF₃(CF₂)₇(CH₂)₂O(CH₂)₃Si(OCH₃)₃CF₃(CF₂)₇(CH₂)O(CH₂)₂Si(OCH₃)₃ CF₃(CF₂)₇CONH(CH₂)₃S(OCH₃)₃CF₃(CF₂)₃O[CF(CF₃)CF(CF₃)O]₂CF(CF₃)—CONH(CH₂)₃Si(OCH₃)₃CF₃(CF₂)₃(CH₂)₂Si(CH₃)(OCH₃)₂ CF₃(CF₂)₅(CH₂)₂Si(CH₃)(OCH₃)₂CF₃(CH₂)₂Si(CH₃)(OCH₃)₂ CF₃(CF₂)₃(CH₂)₃Si(CH₃)(OCH₃)₂CF₃(CF₂)₅(CH₂)₃Si(CH₃)(OCH₃)₂ CF₃(CF₂)₇(CH₂)₃Si(CH₃)(OCH₃)₂CF₃(CF₂)₄(CF₂)₂(CH₂)₂Si(CH₃)(OCH₃)₂ CF₃(CF₂)₄(CF₂)₂(CH₂)₃Si(CH₃)(OCH₃)₂CF₃(CF₂)₄(CH₂)₂O(CH₂)₃Si(CH₃)(OCH₃)₂ CF₃(CF₂)₇CONH(CH₂)₂Si(CH₃)(OCH₃)₂CF₃(CF₂)₇CONH(CH₂)₃Si(CH₃)(OCH₃)₂CF₃(CF₂)₃O[CF(CF₃)CF(CF₃)O]₂CF(CF₃)—CONH(CH₂)₃Si(CH₃)(OCH₃)₂CH₃(CH₂)₇Si(OCH₃)₃ CH₃(CF₂)₇(CH₂)₂Si(OCH₃)₃CH₃(CF₂)₇(CH₂)₂Si(CH₃)(OCH₃)₂ CH₃(CF₂)₇(CH₂)₂Si(OCH₃)₃CH₃(CF₂)₇(CH₂)₂Si(NCO)₃ CH₃(CF₂)₈(CH₂)₂Si(OCH₃)₃ CH₃(CF₂)₈(CH₂)₂Si(NCO)₃CH₃(CF₂)₉(CH₂)₂Si(OCH₃)₃ CH₃(CF₂)₉(CH₂)₂Si(NCO)₃CH₃CH₂(CF₂)₆(CH₂)₂Si(OCH₃)₃ CH₃CH₂(CF₂)₆(CH₂)₂Si(NCO)₃CH₃CH₂(CF₂)₈(CH₂)₂Si(OCH₃)₃ CH₃CH₂(CF₂)₈(CH₂)₂Si(NCO)₃CH₃CH₂(CF₂)₁₀(CH₂)₂Si(OCH₃)₃ CH₃(CF₂)₄₀(CF₂)₂(CH₂)₂Si(OCH₃)₃CH₃(CF₂)₇(CH₂)₂O(CH₂)₃Si(OCH₃)₃ CH₃(CF₂)₈(CH₂)₂O(CH₂)₃Si(OCH₃)₃CH₃(CF₂)₉(CH₂)₂—O—(CH₂)₃Si(OCH₃)₃ CH₃CH₂(CF₂)₆(CH₂)₂O(CH₂)₃Si(OCH₃)₃CH₃(CF₂)₆CONH(CH₂)₃Si(OCH₃)₃ CH₃(CF₂)₆CONH(CH₂)₃Si(OCH₃)₃CH₃(CF₂)₃O[CF(CF₃)CF(CF₃)O]₂CF(CF₃)—CONH(CH₂)₃Si(OM₃)₃

These compounds can be used either alone, or in combinations of two ormore different compounds.

There are no particular restrictions on the catalyst capable ofinteracting with the metal-based surfactant that is incorporated withinthe solution (a), provided it is capable of generating an interactionvia coordination bonding or hydrogen bonding with either the metalportion or the hydrolyzable group portion of the metal-based surfactant,thereby activating the hydrolyzable group or hydroxyl group, andpromoting a condensation. Of the possible catalysts, at least onecompound selected from a group consisting of metal oxides; metalhydroxides; metal alkoxides; chelated or coordinated metal compounds;partial hydrolysis products of metal alkoxides; hydrolysis productsobtained by treating a metal alkoxide with a two-fold or greaterequivalence of water; organic acids; silanol condensation catalysts, andacid catalysts is preferred, and metal alkoxides and partial hydrolysisproducts of metal alkoxides are particularly desirable.

There are no particular restrictions on the metal within these metaloxides; metal hydroxides; metal alkoxides; chelated or coordinated metalcompounds; partial hydrolysis products of metal alkoxides; hydrolysisproducts obtained by treating a metal alkoxide with a two-fold orgreater equivalence of water; and silanol condensation catalysts, and atleast one metal selected from a group consisting of titanium, zirconium,aluminum, silicon, germanium, indium, tin, tantalum, zinc, tungsten, andlead is preferred, although titanium, zirconium, aluminum or silicon iseven more preferred, and titanium is particularly desirable.

Metal oxides in sol, gel, or solid form can be used. There are noparticular restrictions on the method used for producing a gel or sol,and taking a silica sol as an example, suitable methods include cationexchange of a sodium silicate solution, and hydrolysis of a siliconalkoxide. Sols that are dispersed stably within an organic solvent arepreferred, and sols in which the particle diameter is within a rangefrom 10 to 100 nm, and even more preferably from 10 to 20 nm, areparticularly desirable. There are no particular restrictions on the solshape, and spherical or elongated shapes can be used.

Specific examples of suitable sols include methanol silica sol, IPA-ST,IPA-ST-UP, IPA-ST-ZL, NPC-ST-30, DMAC-ST, MEK-ST, MIBK-ST, XBA-ST, ANDPMA-ST (all of which are brand names of organosilica sols manufacturedby Nissan Chemical Industries, Ltd.)

There are no particular restrictions on the quantity of metal oxideused, provided it has no effect on the formed chemically adsorbed film,but the use of a quantity that is catalytic relative to the metal-basedsurfactant is preferred, and an oxide-equivalent quantity of 0.001 to 1mol, and even more preferably from 0.001 to 0.2 mots, per 1 mol of themetal-based surfactant is particularly desirable. These metal oxides canbe used either alone, or in combinations of two or more differentcompounds.

Suitable metal hydroxides include those produced by any appropriatemethod, provided the product is a hydroxide of a metal. Examples ofsuitable methods for producing metal hydroxides include hydrolyzing thetypes of metal alkoxides described below, and reacting a metal salt witha metal hydroxide. Furthermore, commercially available metal hydroxidesmay also be purified and used if desired.

There are no particular restrictions on the number of carbon atomswithin the alkoxy group of the metal alkoxide, although from theviewpoints of oxide concentration, ease of eliminating organic matter,and availability, alkoxy groups of 1 to 4 carbon atoms are preferred.Specific examples of the metal alkoxides used in the present inventioninclude silicon alkoxides such as Si(OCH₃)₄, Si(OC₂H₅)₄, Si(OC₃H₇-i)₄,and Si(OC₄H₉-t)₄; titanium alkoxides such as Ti(OCH₃)₄, Ti(OC₂H₅)₄,Ti(OC₃H₇-i)₄, and Ti(OC₄H₉)₄; tetrakistrialkylsiloxy titanium compoundssuch as Ti[OSi(CH₃)₃]₄ and Ti[OSi(C₂H₅)₃]₄; zirconium alkoxides such asZr(OCH₃)₄, Zr(OC₂H₅)₄, Zr(OC₃H₇)₄, and Zr(OC₄H₉)₄; aluminum alkoxidessuch as Al(OCH₃)₄, Al(OC₂H₅)₄, Al(OC₃H₇-i)₄, and Al(OC₄H₉)₃; germaniumalkoxides such as Ge(OC₂H₅)₄; indium alkoxides such as In(OCH₃)₃,In(OC₂H₅)₃, In(OC₃H₇-i)₃, and In(OC₄H₉)₃; tin alkoxides such asSn(OCH₃)₄, Sn(OC₂H₅)₄, Sn(OC₃H₇-i)₄, and Sn(OC₄H₉)₄; tantalum alkoxidessuch as Ta(OCH₃)₅, Ta(OC₂H₅)₅, Ta(OC₃H₇-i)₅, and Ta(OC₄H₉)₅; tungstenalkoxides such as W(OCH₃)₆, W(OC₂H₅)₆, W(OC₃H₇-i)₆, and W(OC₄H₉)₆; zincalkoxides such as Zn(OC₂H₅)₂; and lead alkoxides such as Pb(OC₄H₉)₄.These alkoxides can be used either alone, or in combinations of two ormore different compounds.

Furthermore, in the present invention, a composite alkoxide obtained byreacting together two or more metal alkoxides, a composite alkoxideobtained by reacting one or more metal alkoxides with one or more metalsalts, or a combination of these composite alkoxides, can also be usedas the metal alkoxide.

Examples of composite alkoxides obtained by reacting together two ormore metal alkoxides include those composite alkoxides obtained byreacting an alkali metal or alkali earth metal alkoxide with atransition metal alkoxide, and composite alkoxides obtained as complexsalts by combining elements from group 3B.

Specific examples include BaTi(OR)₆, SrTi(OR)₆, BaZr(OR)₆, SrZr(OR)₆,LiNb(OR)₆, LiTa(OR)₆, and combinations thereof, as well as products ofreaction between a silicon alkoxide and an aforementioned metalalkoxide, and condensation products thereof, such as LiVO(OR)₄,MgAl₂(OR)₈, (RO)₃SiOAl(OR′)₂, (RO)₃SiOTi(OR′)₃, (RO)₃SiOZr(OR′)₃,(RO)₃SiOB(OR')₂, (RO)₃SiONb(OR′)₄, and (RO)₃SiOTa(OR′)₄. In theseformulas, R and R′ represents alkyl groups.

Examples of composite alkoxide obtained by reacting one or more metalalkoxides with one or more metal salts include compounds obtained byreacting a metal salt with a metal alkoxide.

Examples of suitable metal salts include chlorides, nitrates, sulfates,acetates, formates, and oxalates, whereas examples of suitable metalalkoxides include the same metal alkoxides as those listed above.

There are no particular restrictions on the quantity of metal alkoxideused, provided it has no effect on the formed chemically adsorbed film,but the use of a quantity that is catalytic relative to the metal-basedsurfactant is preferred, and a quantity within a range from 0.001 to 1mol, and preferably from 0.001 to 0.2 mols, or an oxide-equivalentwithin a range from 0.001 to 1 mol, and preferably from 0.001 to 0.2mols, per 1 mol of the metal-based surfactant is particularly desirable.These metal alkoxides can be used either alone, or in combinations oftwo or more different compounds.

Partial hydrolysis products of metal alkoxides are products obtainedprior to complete hydrolysis of the metal alkoxide, and examples includemetal oxide sol precursors, or oligmers.

Specific examples include dispersoids that are able to be stablydispersed in an organic solvent without aggregating, even in the absenceof acids, bases, and/or dispersion stabilizers. These dispersoids referto fine particles dispersed within the dispersion system, and referspecifically to colloidal particles and the like. Here, the phrase“stably dispersed without aggregating” means that within the organicsolvent, in the absence of acids, bases, and/or dispersion stabilizers,the hydrolysis product dispersoids do not aggregate to form aheterogeneous system, but rather form a uniform system that ispreferably transparent. Here, the term “transparent” means that thetransmittance of visible light is high, and specifically, refers to astate wherein if the oxide-equivalent concentration of the dispersoid isset to 0.5% by weight, a quartz cell with an optical path length of 1 cmis used, neat organic solvent is used as a comparative sample, and themeasurements are conducted using light with a wavelength of 550 nm, thenthe spectral transmittance is preferably within a range from 80 to 100%.There are no particular restrictions on the particle diameter of thehydrolysis product dispersoid, although in order to achieve a hightransmittance relative to visible light, the particle diameter istypically within a range from 1 to 100 nm, and preferably from 1 to 50nm, and even more preferably from 1 to 10 nm. Acids, bases, anddispersion stabilizers are discussed below.

One example of a favorable method for producing a partial hydrolysisproduct of a metal alkoxide is a method in which an aforementioned metalalkoxide is hydrolyzed in an organic solvent, in the absence of acids,bases, and/or dispersion stabilizers, using from 0.5 to less than 2.0mols of water per 1 mol of the metal alkoxide, at a temperature within arange from −100° C. to the reflux temperature of the organic solvent.

Specifically, suitable methods include the following:

(1) a method in which from 0.5 to 1.0 mols of water per 1 mol of themetal alkoxide is added to an organic solvent in the absence of acids,bases, and/or dispersion stabilizers,(2) a method in which from 1.0 to less than 2.0 cools of water per 1 molof the metal alkoxide is added to an organic solvent, in the absence ofacids, bases, and/or dispersion stabilizers, and at a temperature thatis no higher than that required to initiate hydrolysis, or at atemperature of no more than 0° C., and preferably at a temperaturewithin a range from −50 to −100° C., and(3) a method in which from 0.5 to less than 2.0 mols of water per 1 molof the metal alkoxide is added to an organic solvent at roomtemperature, in the absence of acids, bases, and/or dispersionstabilizers, but with the rate of the hydrolysis reaction controlled,either by controlling the rate of addition of the water, or by loweringthe concentration of the added water by dilution with a water-solublesolvent or the like.

In the method (1) described above, treatment is conducted with apredetermined quantity of water at an arbitrary temperature, and thenadditional water is added and reacted at a temperature that is no higherthan that required to initiate hydrolysis, or at a temperature of nomore than −20° C.

The reaction between the metal alkoxide and water can be conductedwithout using an organic solvent, by simply mixing the metal alkoxideand the water directly, but is preferably conducted in an organicsolvent. Specifically, the reaction can be conducted either by a methodin which water diluted with the organic solvent is added to an organicsolvent solution of the metal alkoxide, or a method in which the metalalkoxide or an organic solvent solution thereof is added to an organicsolvent containing suspended or dissolved water, although the formermethod, in which the water is added afterwards, is preferred.

There are no particular restrictions on the water used, provided it isneutral, although the use of pure water or distilled water is preferred.There are no particular restrictions on the quantity of water used,provided it satisfies the prescribed range described above, and thequantity can be selected so as to achieve a dispersoid with the desiredproperties.

There are no particular restrictions on the concentration of the metalalkoxide within the organic solvent, provided the concentration inhibitsrapid heat generation and provides a suitable level of fluidity toenable stirring, although a concentration within a range from 5 to 30%by weight is typical.

In the method (1) described above, there are no particular restrictionson the reaction temperature for the reaction between the metal alkoxideand water, although a typical temperature is within a range from −100 to+100° C., and a temperature within a range from −20° C. to the boilingpoint of either the organic solvent used or the alcohol produced by thehydrolysis reaction.

In the method (2) described above, the temperature at which the water isadded varies depending on the stability of the metal alkoxide used, andalthough there are no particular restrictions provided the temperatureis either no higher than the hydrolysis initiation temperature or nohigher than 0° C., the addition of the water to the metal alkoxide ispreferably conducted at a temperature within a range from −50° C. to−100° C., with the actual temperature dependent on the nature of themetal alkoxide being used. Furthermore, the reaction can also beconducted by adding the water at a low temperature, allowing the mixtureto age for a certain period, subsequently conducting hydrolysis at atemperature within a range from room temperature to the refluxtemperature of the solvent, and then conducting a dehydrationcondensation reaction.

In the method (3) described above, the reaction between the metalalkoxide and water is conducted at a cooled temperature that can beachieved without special cooling equipment, for example, a temperaturewithin a range from 0° C. to room temperature, and the hydrolysis rateis controlled using a factor other than temperature, such as bycontrolling the rate of addition of the water. Reaction can also beconducted allowing the mixture to age for a certain period, subsequentlyconducting hydrolysis at a temperature within a range from roomtemperature to the reflux temperature of the solvent, and thenconducting a dehydration condensation reaction.

The organic solvent used is preferably capable of dispersing thehydrolysis product of the metal alkoxide as a dispersoid, and becausethe reaction for treating the metal-based surfactant with water can beconducted at low temperatures, a solvent that exhibits high watersolubility and does not freeze at low temperatures is preferred.

Specific examples of suitable solvents include alcohols such asmethanol, ethanol, and isopropanol; halogenated hydrocarbon-basedsolvents such as methylene chloride, chloroform, and chlorobenzene;hydrocarbon-based solvents such as hexane, cyclohexane, benzene,toluene, and xylene; ether-based solvents such as tetrahydrofuran,diethyl ether, and dioxane; ketone-based solvents such as acetone,methyl ethyl ketone, and methyl isobutyl ketone; amide-based solventssuch as dimethylformamide and N-methylpyrrolidone; sulfoxide-basedsolvents such as dimethylsulfoxide; and silicones such asmethylpolysiloxane, octamethylcyclotetrasiloxane,decamethylcyclopentasiloxane, and methylphenylpolysiloxane (for example,see Japanese Unexamined Patent Application, First Publication No. Hei9-208438).

These solvents can be used either alone, or in mixtures of two or moredifferent solvents.

In the case of a mixed solvent, a combination of a hydrocarbon-basedsolvent such as toluene or xylene, and a lower alcohol-based solventsuch as methanol, ethanol, isopropanol, or t-butanol is preferred. Insuch cases, the use of a secondary or higher alcohol-based solvent suchas isopropanol or t-butanol as the lower alcohol-based solvent isparticularly preferred. There are no particular restrictions on themixing ratio of the mixed solvent, although the use of ahydrocarbon-based solvent and a lower alcohol-based solvent in avolumetric ratio within a range from 99/1 to 50/50 is preferred.

Furthermore, in the hydrolysis of the metal alkoxide by water, an acid,base, or dispersion stabilizer may also be added. There are noparticular restrictions on the acid or base added, provided it functionsas a deflocculant for re-dispersing any precipitate that settles out, oras a catalyst for the hydrolysis and dehydration condensation of themetal alkoxide to produce a dispersoid of colloidal particles or thelike, and as a dispersing agent for the produced dispersoid.

In such cases, there are no particular restrictions on the acid or base,provided it functions as a deflocculant for re-dispersing anyprecipitate that settles out, or as mentioned above, as a catalyst forthe hydrolysis and dehydration condensation of the metal alkoxide toproduce a dispersoid of colloidal particles or the like, and as adispersing agent for the produced dispersoid.

Examples of suitable acids include mineral acids such as hydrochloricacid, nitric acid, boric acid, and fluoroboric acid; organic acids suchas acetic acid, formic acid, oxalic acid, carbonic acid, trifluoroaceticacid, p-toluenesulfonic acid, and methanesulfonic acid; and photoacidgenerators that generate acid on irradiation such as diphenyliodoniumhexafluorophosphate and triphenylsulfonium hexafluorophosphate.

Examples of suitable bases include triethanolamine, triethylamine,1,8-diazabicyclo[5.4.0]-7-undecene, ammonia, dimethylformamide, andphosphine.

Examples of suitable dispersion stabilizers include reagents that areeffective in dispersing the dispersoid stably within the dispersionmedium, and coagulation inhibitors such as deflocculants, protectivecolloids, and surfactants. Specific examples include polyvalentcarboxylic acids such as glycolic acid, gluconic acid, lactic acid,tartaric acid, citric acid, malic acid, and succinic acid;hydroxycarboxylic acids; phosphoric acids such as pyrophosphoric acidand tripolyphosphoric acid; polydentate ligand compounds that exhibit apowerful chelating effect relative to metal atoms, such asacetylacetone, methyl acetoacetate, ethyl acetoacetate, n-propylacetoacetate, isopropyl acetoacetate, n-butyl acetoacetate, sec-butylacetoacetate, t-butyl acetoacetate, 2,4-hexanedione, 2,4-heptanedione,3,5-heptanedione, 2,4-octanedione, 2,4-nonaedione, and5-methylhexanedione; aliphatic amine-based and hydrostearic acid-basedpolyesteramines such as Solsperse 3000, 9000, 17000, 20000, and 24000(all manufactured by Zeneca Inc.), and Disperbyk-161, -162, -163, and-164 (all manufactured by BYK-Chemie GmbH); and silicone compounds suchas dimethylpolysiloxane-methyl(polysiloxyalkylene)siloxane copolymers,trimethylsiloxysilicic acid, carboxy-modified silicone oil, andamine-modified silicone (see Japanese Unexamined Patent Application,First Publication No. Hei 9-208438 and Japanese Unexamined PatentApplication, First Publication No. 2000-53421).

There are no particular restrictions on the quantity used of the metalalkoxide partial hydrolysis product, provided it has no effect on theformed organic thin film, but the use of a quantity that is catalyticrelative to the metal-based surfactant is preferred, and anoxide-equivalent quantity of 0.001 to 1 mol, and even more preferablyfrom 0.001 to 0.2 mols, per 1 mol of the metal-based surfactant isparticularly desirable. These metal alkoxide partial hydrolysis productscan be used either alone, or in combinations of two or more differentcompounds.

A metal alkoxide hydrolysis product used in the present invention is aproduct obtained by hydrolyzing a metal oxide with a two-fold or greaterequivalence of water.

This hydrolysis product may be either obtained by hydrolyzing a metalalkoxide with a two-fold or greater equivalence of water, or byproducing a partial hydrolysis product of the metal alkoxide byconducting hydrolysis with a quantity of water less than a two-foldequivalence relative to the metal alkoxide, and then further hydrolyzingthat partial hydrolysis product with an additional predeterminedquantity of water (so that when added to the quantity of water used inthe partial hydrolysis, the total quantity of water is a two-fold orgreater equivalence relative to the metal alkoxide).

The reaction between the metal alkoxide and water can be conductedwithout using an organic solvent, by simply mixing the metal alkoxideand the water directly, although in the present invention, the metalalkoxide and water are preferably reacted together in an organicsolvent.

There are no particular restrictions on the water used, provided it isneutral, although from the viewpoints of minimizing impurities andachieving a dense organic thin film, the use of pure water, distilledwater, or ion exchange water is preferred.

The quantity of water used is preferably a two-fold or greaterequivalence relative to the metal alkoxide, and preferably a 2.0 to8-fold equivalence, and most preferably a 3 to 5-fold equivalence.

Suitable methods of reacting a metal alkoxide and water within anorganic solvent include the following:

(1) a method in which either water, or water that has been diluted withan organic solvent, is added to an organic solvent solution of the metalalkoxide, and(2) a method in which the metal alkoxide or an organic solvent solutionthereof is added to an organic solvent containing suspended or dissolvedwater. In this case, there are no particular restrictions on theconcentration of the metal alkoxide within the organic solvent, providedthe concentration inhibits rapid heat generation and provides a suitablelevel of fluidity to enable stirring, although a concentration within arange from 5 to 30% by weight is preferred.

The organic solvent used is preferably capable of dispersing thehydrolysis product of the metal alkoxide as a dispersoid, and specificexamples include the same organic solvents as those listed in relationto partial hydrolysis products of metal alkoxides.

Furthermore, in addition to the organic solvent, the use of water,acids, bases, or dispersion stabilizers with the hydrolysis product isalso as described above in relation to partial hydrolysis products, andthe same compounds can be used with no particular restrictions.

The metal alkoxide hydrolysis reaction temperature varies depending onfactors such as the reactivity and stability of the metal alkoxide used,but is typically within a range from −100° C. to the reflux temperatureof the organic solvent, and is preferably within a range from −100° C.to −20° C. Hydrolysis can also be conducted by adding the water at a lowtemperature, allowing the mixture to age for a certain period, and thenraising the temperature of the reaction liquid to a temperature within arange from room temperature to the reflux temperature of the solvent toeffect the hydrolysis and dehydration condensation reaction.

Chelated or coordinated metal compounds can be produced by taking asolution of a metal compound, and then adding a chelating agent orcoordination compound that is capable of forming a complex with themetal of the metal compound. There are no particular restrictions on thechelating agents or coordination compounds used, provided they arecapable of chelating or coordinating the metal of metal hydroxides,metal alkoxides, or hydrolysis products obtained by treating metalalkoxides with water, thereby forming a complex.

Specific examples of suitable chelating agents or coordination compoundsinclude saturated aliphatic carboxylic acids such as acetic acid,propionic acid, butyric acid, valeric acid, lauric acid, myristic acid,palmitic acid, and stearic acid; saturated aliphatic dicarboxylic acidssuch as oxalic acid, malonic acid, succinic acid, glutaric acid, adipicacid, pimelic acid, suberic acid, azelaic acid, and sebacic acid;unsaturated carboxylic acids such as acrylic acid, methacrylic acid,crotonic acid, aleic acid, and maleic acid; aromatic carboxylic acidssuch as benzoic acid, toluic acid, and phthalic acid; halogenocarboxylicacids such as chloroacetic acid and trifluoroacetic acid; β-diketonessuch as acetylacetone, benzoylacetone, and hexafluoroacetylacetone;β-ketoesters such as methyl acetoacetate and ethyl acetoacetate; andheterocyclic compounds such as tetrahydrofuran, furan, furancarboxylicacid, thiophene, thiophenecarboxylic acid, pyridine, nicotinic acid, andisonicotinic acid. These compounds can be used either alone, or incombinations of two or more different compounds.

The quantity added of the chelating agent or coordination compound istypically within a range from 0.1 to 10 mols, and preferably from 0.3 to2 mols, and even more preferably from 0.5 to 1.2 mols, per 1 mol ofmetal within the metal hydroxide metal alkoxide, or hydrolysis productobtained by treating a metal alkoxide with water.

Following addition of the chelating agent or coordination compound, asolution of the metal complex can be obtained by stirring the combinedmixture thoroughly. The temperature at which this stirring is conductedis typically within a range from 0° C. to the boiling point of thesolvent being used. The stirring time is typically within a range fromseveral minutes to several hours. The chelated or coordinated metalcompound can be isolated prior to use, or the chelated or coordinatedmetal compound solution obtained on addition of the chelating agent orcoordination compound to the solution of the metal compound can simplybe used. Furthermore, the prepared solution of the chelated orcoordinated metal compound can also be stored.

Examples of suitable silanol condensation catalysts include carboxylicacid metal salts, carboxylate metal salts, carboxylic acid metal saltpolymers, carboxylic acid metal salt chelates, titanate esters, andtitanate ester chelates. Specific examples include stannous acetate,dibutyltin dilaurate, dibutyltin dioctate, dibutyltin diacetate,dioctyltin dilaurate, dioctyltin dioctate, dioctyltin diacetate,stannous dioctanoate, lead naphthenate, cobalt naphthenate, iron2-ethylhexanoate, dioctyltin bisoctylthioglycolate, dioctyltin maleate,dibutyltin maleate polymer, dimethyltin mercaptopropionate polymer,dibutyltin bisacetylacetate, dioctyltin bisacetyllaurate, titaniumtetraethoxide, titanium tetrabutoxide, titanium tetraisopropoxide, andtitanium bis(acetylacetonyl)dipropoxide.

Examples of the organic acids that can be used in the present inventioninclude saturated aliphatic monocarboxylic acids such as formic acid,acetic acid, propionic acid, butyric acid, isobutyric acid, valericacid, isovaleric acid, pivalic acid, hexanoic acid, octanoic acid,decanoic acid, lauric acid, myristic acid, palmitic acid, and stearicacid; saturated aliphatic dicarboxylic acids such as oxalic acid,malonic acid, succinic acid, glutaric acid, and adipic acid; unsaturatedaliphatic monocarboxylic acids such as acrylic acid, propiolic acid,methacrylic acid, crotonic acid, isocrotonic acid, and oleic acid;unsaturated aliphatic dicarboxylic acids such as fumaric acid and maleicacid; aromatic carboxylic acids such as benzoic acid, 4-chlorobenzoicacid, and naphthalenecarboxylic acid; aliphatic carboxylic acids thathave been substituted with a halogen atom, such as monochloroacetic acidand trifluoroacetic acid; hydroxycarboxylic acids such as glycolic acid,lactic acid, malic acid, and citric acid; aliphatic carboxylic acidsthat have been substituted with an aromatic group, such as phenylaceticacid and 3-phenylpropionic acid; and sulfonic acids such asbenzenesulfonic acid, p-toluenesulfonic acid, and methanesulfonic acid.

Of these organic acids, from the viewpoints of providing excellentactivation of the hydrolyzable group of the metal-based surfactant, andease of handling, organic acids with a pKa value (the negative of thelog of the acid dissociation constant) within a range from 1 to 6 arepreferred, and organic acids with a pKa value from 2 to 5 areparticularly desirable.

The acid dissociation constant Ka can be measured accurately bypotentiometry, using a variety of different electrodes such as glasselectrodes, metal electrodes, metal amalgam electrodes,oxidation-reduction electrodes, and ion selective electrodes. In thepresent invention, the acid dissociation constant Ka can be determinedby measuring the pH within an aqueous solution (or in the case ofmaterials that are insoluble in water, within a mixed solvent of waterand a suitable organic solvent, or within a suitable organic solvent).Depending on the measurement conditions, the pKa value may vary byapproximately ±0.3. The acid dissociation constants Ka and pKa valuesfor a variety of organic acids are disclosed in A. E. Martell, R. M.Smith, Critical Stability Constants, Vol. 1, 2, 3, 5, Plenum Press(1974, 1975, 1977, 1982).

Examples of suitable acid catalysts include mineral acids such ashydrochloric acid, nitric acid, boric acid, and fluoroboric acid,organic acids such as acetic acid, formic acid, oxalic acid, carbonicacid, trifluoroacetic acid, p-toluenesulfonic acid, and methanesulfonicacid, and photoacid generators that generate acid on irradiation such asdiphenyliodonium hexafluorophosphate and triphenylsulfoniumhexafluorophosphate.

There are no particular restrictions on the metal-based surfactanthaving at least one hydroxyl group that is used within theaforementioned solution (b), provided the surfactant contains at leastone hydroxyl group and a hydrophobic group within the same molecule.Specific examples of this type of metal-based surfactant include thecompounds represented by the aforementioned formula (III).

In the formula (III), R¹, M, X, n, and m are as defined above. In thosecases where (m−n−1) is 2 or greater, the X groups may be the same ordifferent.

Furthermore, in addition to the metal-based surfactant having at leastone hydroxyl group, the solution (b) may also contain a catalyst capableof interacting with the metal-based surfactant. Examples of thiscatalyst include the same catalysts as those used in the aforementionedsolution (a).

Specific examples of compounds represented by the formula (III) includethose listed below. In the following examples, compounds in which themetal atom M is a silicon atom are shown as representative examples, butthe present invention is not limited to these cases.

CH₃CH₂O(CH₂)₁₅Si(OCH₃)(OH)₂ CF₃CH₂O(CH₂)₁₅Si(OCH₃)₁(OH)₂CH₃(CH₂)₂Si(CH₃)₂(CH₂)₁₅Si(OCH₃)(OH)₂CH₃(CH₂)₆Si(CH₃)₂(CH₂)₉Si(OCH₃)(OH)₂ CH₃COO(CH₂)₁₅Si(OCH₃)(OH)₂CF₃(CF₂)₅(CH₂)₂Si(OCH₃)(OH)₂ CF₃(CF₂)₇(CH═CH)₃Si(OCH₃)(OH)₂CH₃CH₂O(CH₂)₁₅Si(OC₂H₅)(OH)₂ CH₃(CH₂)₂Si(CH₃)₂(CH₂)₁₅Si(OC₂H₅)(OH)₂CH₃(CH₂)₆Si(CH₃)₂(CH₂)₉Si(OC₂H₅)(OH)₂CF₃(CH₂)₆Si(CH₃)₂(CH₂)₉Si(OC₂H₅)(OH)₂ CH₃COO(CH₂)₁₅Si(OC₂H₅)(OH)₂CF₃COO(CH₂)₁₅Si(OC₂H₅)(OH)₂ CF₃COO(CH₂)₁₅Si(OCH₃)(OH)₂CF₃(CF₂)₉(CH₂)₂Si(OC₂H₅)(OH)₂ CF₃(CF₂)₇(CH₂)₂Si(OC₂H₅)(OH)₂CF₃(CF₂)₅(CH₂)₂Si(OC₂H₅)(OH)₂ CF₃(CF₂)₇(CH═CH)₃Si(OC₂H₅)(OH)₂CF₃(CF₂)₉(CH₂)₂Si(OCH₃)(OH)₂ CF₃(CF₂)₅(CH₂)₂Si(OCH₃)(OH)₂CF₃(CF₂)₇(CH₂)₂Si(CH₃)(OH)₂ CF₃(CF₂)₉(CH₂)₂Si(CH₃)(OH)₂CH₃CH₂O(CH₂)₁₅Si(OCH₃)₂(OH) CF₃CH₂—O—(CH₂)₁₅Si(OCH₃)₂(OH)CH₃(CH₂)₂Si(CH₃)₂(CH₂)₁₅Si(OCH₃)₂(OH)CH₃(CH₂)₆Si(CH₃)₂(CH₂)₉Si(OCH₃)₂(OH) CH₃COO(CH₂)₁₅Si(OCH₃)₂(OH)CF₃(CF₂)₅(CH₂)₂Si(OCH₃)₂(OH) CH₃CH₂O(CH₂)₁₅Si(OC₂H₅)₂(OH)CF₃(CF₂)₇(CH═CH)₃Si(OCH₃)₂(OH) CH₃(CH₂)₂Si(CH₃)₂(CH₂)₁₅Si(OC₂H₅)₂(OH)CH₃(CH₂)₆Si(CH₃)₂(CH₂)₉Si(OC₂H₅)₂(OH)CF₃(CH₂)₆Si(CH₃)₂(CH₂)₉Si(OC₂H₅)₂(OH) CH₃COO(CH₂)₁₅Si(OC₂H₅)₂(OH)CF₃COO(CH₂)₁₅Si(OC₂H₅)₂(OH) CF₃COO(CH₂)₁₅SOCH₃)₂(OH)CF₃(CF₂)₉(CH₂)₂Si(OC₂H₅)₂(OH) CF₃(CF₂)₇(CH₂)₂Si(OC₂H₅)₂(OH)CF₃(CF₂)₅(CH₂)₂Si(OC₂H₅)₂(OH) CF₃(CF₂)₇(CH═CH)₃Si(OC₂H₅)₂(OH)CF₃(CF₂)₉(CH₂)₂Si(OCH₃)₂(OH) CF₃ (CF₂)₅(CH₂)₂Si(OCH₃)₂(OH)CF₃(CF₂)₇(CH₂)₂Si(CH₃)(OC₂H₅)(OH) CF₃(CF₂)₇(CH₂)₂Si(CH₃)(OCH₃)(OH)CF₃(CH₂)₂Si(OCH₃)(OH)₂ CF₃(CF₂)₃(CH₂)₂Si(OCH₃)(OH)₂ CF₃(CF₂)₅(CH₂)₂Si(OCH₃)(OH)₂ CF₃(CF₂)₇(CH₂)₂Si(OCH₃)(OH)₂CF₃(CF₂)₃(CH₂)₃Si(OCH₃)(OH)₂ CF₃(CF₂)₅(CH₂)₃Si(OCH₃)(OH)₂CF₃(CF₂)₇(CH₂)₃Si(OCH₃)(OH)₂ CF₃(CF₂)₄O(CF₂)₂(CH₂)₂Si(OCH₃)(OH)₂CF₃(CF₂)₄O(CF₂)₂(CH₂)₃Si(OCH₃)(OH)₂ CF₃(CF₂)₇(CH₂)₂O(CH₂)₃Si(OCH₃)(OH)₂CF₃(CF₂)₇CONH(CH₂)₂Si(OCH₃)(OH)₂ CF₃(CF₂)₇CONH(CH₂)₃Si(OCH₃)(OH)₂CF₃(CF₂)₃O[CF(CF₃)CF(CF₃)O]₂CF(CF₃)CONH(CH₂)₃Si(OCH₃)(OH)₂ CF₃(CH₂)₂Si(OCH₃)₂(OH) CF₃(CF₂)₃(CH₂)₂Si(OCH₃)₂(OH)

CF₃(CF₂)_(s)(CH₂)₂Si(OCH₃)₂(OH)

CF₃(CF₂)₇(CH₂)₂Si(OCH₃)₂(OH) CF₃(CF₂)₃(CH₂)₃Si(OCH₃)₂(OH)CF₃(CF₂)₅(CH₂)₃Si(OCH₃)₂(OH) CF₃(CF₂)₇(CH₂)₃Si(OCH₃)₂(OH)CF₃(CF₂)₄O(CF₂)₂(CH₂)₂Si(OCH₃)₂(OH) CF₃(CF₂)₄O(CF₂)₂(CH₂)₃Si(OCH₃)₂(OH)CF₃(CF₂)₇(CH₂)₂—O—(CH₂)₃Si(OCH₃)₂(OH) CF₃(CF₂)₇CONH(CH₂)₂Si(OCH₃)₂(OH)CF₃(CF₂)₇CONH(CH₂)₃Si(OCH₃)₂(OH)CF₃(CF₂)₃O[CF(CF₃)CF(CF₃)O]₂CF(CF₃)CONH(CH₂)₃Si(OCH₃)₂(OH)CH₃(CH₂)₇Si(OCH₃)(OH)₂ CH₃(CF₂)₇(CH₂)₂Si(OCH₃)(OH)₂CH₃(CF₂)₇(CH₂)₂Si(NCO)(OH)₂ CH₃(CF₂)₈(CH₂)₂Si(OCH₃)(OH)₂CH₃(CF₂)₈(CH₂)₂Si(NCO)(OH)₂ CH₃(CF₂)₉(CH₂)₂Si(OCH₃)(OH)₂CH₃(CF₂)₉(CH₂)₂Si(NCO)(OH)₂ CH₃CH₂(CF₂)₆(CH₂)₂Si(OCH₃)(OH)₂CH₃CH₂(CF₂)₆(CH₂)₂Si(OCH₃)(OH)₂ CH₃CH₂(CF₂)₆(CH₂)₂Si(NCO)(OH)₂CH₃CH₂(CF₂)₈(CH₂)₂Si(OCH₃)(OH)₂ CH₃CH₂(CF₂)₈(CH₂)₂Si(NCO)(OH)₂CH₃CH₂(CF₂)₁₀(CH₂)₂Si(OCH₃)(OH)₂ CH₃(CF₂)₄O(CF₂)₂(CH₂)₂Si(OCH₃)(OH)₂CH₃(CF₂)₇(CH₂)₂—O—(CH₂)₃Si(OCH₃)(OH)₂CH₃(CF₂)₈(CH₂)₂O(CH₂)₃Si(OCH₃)(OH)₂CH₃(CF₂)₉(CH₂)₂—O—(CH₂)₃Si(OCH₃)(OH)₂CH₃CH₂(CF₂)₆(CH₂)₂—O—(CH₂)₃Si(OCH₃)(OH)₂CH₃(CF₂)₆CONH(CH₂)₃Si(OCH₃)(OH)₂ CH₃(CF₂)₈CONH(CH₂)₃Si(OCH₃)(OH)₂CH₃(CF₂)₃O[CF(CF₃)CF(CF₃)O]₂CF(CF₃)CONH(CH₂)₃Si(OCH₃)(OH)₂CF₃(CF₂)₃(CH₂)₂Si(CH₃)(OCH₃)(OH) CF₃(CF₂)₅(CH₂)₂Si(CH₃)(OCH₃)(OH)CF₃(CH₂)₂Si(CH₃)(OCH₃)(OH) CF₃(CF₂)₃(CH₂)₃Si(CH₃)(OCH₃)(OH)CF₃(CF₂)₅(CH₂)₃Si(CH₃)(OCH₃)(OH) CF₃(CF₂)₇(CH₂)₃Si(CH₃)(OCH₃)(OH)CF₃(CF₂)₄(CF₂)₂(CH₂)₂Si(CH₃)(OCH₃)(OH)CF₃(CF₂)₄(CF₂)₂(CH₂)₃Si(CH₃)(OCH₃)(OH)CF₃(CF₂)₄(CH₂)₂—O—(CH₂)₃Si(CH₃)(OCH₃)(OH)CF₃(CF₂)₇CONH(CH₂)₂Si(CH₃)(OCH₃)(OH)CF₃(CF₂)₇CONH(CH₂)₃Si(CH₃)(OCH₃)(OH)CF₃(CF₂)₃O[CF(CF₃)CF(CF₃)O]₂CF(CF₃)CONH(CH₂)₃Si(CH₃)(OCH₃)(OH)CH₃(CH₂)₇Si(OCH₃)₂(OH) CH₃(CF₂)₇(CH₂)₂Si(OCH₃)₂(OH) CH₃(CF₂)₇(CH₂)₂^(Si)(CH₃)(OCH₃)(OH) CH₃(CF₂)₇(CH₂)₂Si(OCH₃)₂(OH)CH₃(CF₂)₇(CH₂)₂Si(NCO)₂(OH) CH₃(CF₂)₈(CH₂)₂Si(OCH₃)₂(OH)CH₃(CF₂)₈(CH₂)₂Si(NCO)₂(OH) CH₃(CF₂)₉(CH₂)₂Si(OCH₃)₂(OH)CH₃(CF₂)₉(CH₂)₂Si(NCO)₂(OH) CH₃CH₂(CF₂)₆(CH₂)₂Si(OCH₃)₂(OH)CH₃CH₂(CF₂)₆(CH₂)₂Si(NCO)₂(OH) CH₃CH₂(CF₂)₈(CH₂)₂Si(OCH₃)₂(OH)CH₃CH₂(CF₂)₈(CH₂)₂Si(NCO)₂(OH) CH₃CH₂(CF₂)₁₀(CH₂)₂Si(OCH₃)₂(OH)CH₃(CF₂)₄₀(CF₂)₂(CH₂)₂Si(OCH₃)₂(OH) CH₃(CF₂)₇(CH₂)₂O(CF₂)₃Si(OCH₃)₂(OH)CH₃(CF₂)₈(CH₂)₂O(CH₂)₃Si(OCH₃)₂(OH) CH₃(CF₂)₉(CH₂)₂O(CH₂)₃Si(OCH₃)₂(OH)CH₃CH₂(CF₂)₆(CH₂)₂O(CH₂)₃Si(OCH₃)₂(OH) CH₃(CF₂)₆CONH(CH₂)₃Si(OCH₃)₂(OH)CH₃(CF₂)₈CONH(CH₂)₃Si(OCH₃)₂(OH)CH₃(CF₂)₃O[CF(CF₃)CF(CF₃)O]₂CF(CF₃)CONH(CH₂)₃Si(OCH₃)₂(OH)CH₃CH₂O(CH₂)₁₅Si(OH)₃ CF₃CH₂O(CH₂)₁₅Si(OH)₃CH₃(CH₂)₂Si(CH₃)₂(CH₂)₁₅Si(OH)₃ CH₃(CH₂)₆Si(CH₃)₂(CH₂)₉Si(OH)₃CH₃COO(CH₂))₅Si(OH)₃ CF₃(CF₂)₅(CH₂)₂Si(OH)₃ CF₃(CF₂)₇(CH═CH)₃Si(OH)₃CH₃CH₂O(CH₂)₁₅Si(OH)₃ CH₃(CH₂)₂Si(CH₃)₂(CH₂)₁₅Si(OH)₃CH₃(CH₂)₆Si(CH₃)₂(CH₂)₉Si(OH)₃ CF₃(CH₂)₆Si(CH₃)₂(CH₂)₉Si(OH)₃CH₃COO(CH₂)₁₅Si(OH)₃ CF₃COO(CH₂)₁₅Si(OH)₃ CF₃(CF₂)₉(CH₂)₂Si(OH)₃CF₃(CF₂)₇(CH₂)₂Si(OH)₃ CF₃(CF₂)₅(CH₂)₂Si(OH)₃ CF₃(CF₂)₇(CH═CH)₃Si(OH)₃CF₃(CF₂)₉(CH₂)₂Si(OH)₃ CF₃(CF₂)₅(CH₂)₂Si(OH)₃CF₃(CF₂)₇(CH₂)₂Si(CH₃)₂(OH) CF₃(CH₂)₂Si(OH)₃ CF₃(CF₂)₃(CH₂)₂Si(OH)₃CF₃(CF₂)₅(CH₂)₂Si(OH)₃ CF₃(CF₂)₇(CH₂)₂Si(OH)₃ CF₃(CF₂)₃(CH₂)₃Si(OH)₃CF₃(CF₂)₅(CH₂)₃Si(OH)₃ CF₃(CF₂)₇(CH₂)₃Si(OH)₃CF₃(CF₂)₄O(CF₂)₂(CH₂)₂Si(OH)₃ CF₃(CF₂)₄O(CF₂)₂(CH₂)₃Si(OH)₃CF₃(CF₂)₇(CH₂)₂O(CH₂)₃Si(OH)₃ CF₃ (CF₂)₇CONH(CH₂)₂Si(OH)₃CF₃(CF₂)₇CONH(CH₂)₃Si(OH)₃CF₃(CF₂)₃O[CF(CF₃)CF(CF₃)O]₂CF(CF₃)CONH(CH₂)₃Si(OH)₃ CH₃(CH₂)₇Si(OH)₃CH₃(CF₂)₇(CH₂)₂Si(OH)₃ CH₃(CF₂)₇(CH₂)₂Si(OH)₃ CH₃(CF₂)₈(CH₂)₂Si(OH)₃CH₃(CF₂)₉(CH₂)₂Si(OH)₃ CH₃CH₂(CF₂)₆(CH₂)₂Si(OH)₃CH₃CH₂(CF₂)₈(CH₂)₂Si(OH)₃ CH₃CH₂(CF₂)₁₀(CH₂)₂Si(OH)₃CH₃(CF₂)₄₀(CF₂)₂(CH₂)₂Si(OH)₃ CH₃(CF₂)₇(CH₂)₂O(CH₂)₃Si(OH)₃CH₃(CF₂)₈(CH₂)₂O(CH₂)₃Si(OH)₃ CH₃(CF₂)₉(CH₂)₂O(CH₂)₃Si(OH)₃CH₃CH₂(CF₂)₆(CH₂)₂O(CH₂)₃Si(OH)₃ CH₃(CF₂)₆CONH(CH₂)₃Si(OH)₃CH₃(CF₂)₈CONH(CH₂)₃Si(OH)₃CH₃(CF₂)₃O[CF(CF₃)CF(CF₃)O]₂CF(CF₃)CONH(CH₂)₃Si(OH)₃ CF₃(CF₂)₃(CH₂)₂Si(CH₃)(OH)₂ CF₃(CF₂)₅(CH₂)₂Si(CH₃)(OH)₂CF₃(CH₂)₂Si(CH₃)(OH)₂ CF₃(CF₂)₃(CH₂)₃Si(CH₃)(OH)₂CF₃(CF₂)₅(CH₂)₃Si(CH₃)(OH)₂ CF₃(CF₂)₇(CH₂)₃Si(CH₃)(OH)₂CF₃(CF₂)₄(CF₂)₂(CH₂)₂Si(CH₃)(OH)₂ CF₃(CF₂)₄(CF₂)₂(CH₂)₃Si(CH₃)(OH)₂CF₃(CF₂)₄(CH₂)₂—O—(CH₂)₃Si(CH₃)(OH)₂ CF₃(CF₂)₇CONH(CH₂)₂Si(CH₃)(OH)₂CF₃(CF₂)₇CONH(CH₂)₃Si(CH₃)(OH)₂CF₃(CF₂)₃O[CF(CF₃)CF(CF₃)O]₂CF(CF₃)CONH(CH₂)₃Si(CH₃)(OH)₂CH₃(CF₂)₇(CH₂)₂Si(CH₃)(OH)₂

These compounds can be used either alone, or in combinations of two ormore different compounds.

The organic solvent used in the solution (a) and the solution (b) ispreferably a hydrocarbon-based solvent, a fluorocarbon-based solvent, ora silicone-base solvent, and hydrocarbon-based solvents are particularlypreferred. Solvents with a boiling point within a range from 100 to 250°C. are particularly desirable.

Specific examples of suitable solvents include hydrocarbon-basedsolvents such as n-hexane, cyclohexane, benzene, toluene, xylene,petroleum naphtha, solvent naphtha, petroleum ether, petroleum benzin,isoparaffin, normal paraffin, decalin, industrial gasoline, kerosene,and ligroin; fluorocarbon-based solvents, including Freon-based solventssuch as CBr₂ClCF₃, CClF₂CF₂CCl₃, CClF₂CF₂CHFCl, CF₃CF₂CHCl₂,CF₃CBrFCBrF₂, CClF₂CClFCF₂CCl₃, Cl(CF₂CFCl)₂Cl, Cl(CF₂CFCl)₂CF₂CCl₃, andCl(CF₂CFCl)₃Cl, as well as Florinate (a product of 3M Corporation) andAfrude (a product of Asahi Glass Co., Ltd.); and silicone-based solventssuch as dimethylsilicone, phenylsilicone, alkyl-modified silicone, andpolyether silicone. These solvents can be used either alone, or incombinations of two or more different solvents.

There are no particular restrictions on the quantity of the metal-basedsurfactant in the organic solvent solution, although in order to producea dense, monomolecular film, the quantity of the metal-based surfactantis preferably within a range from 0.1 to 30% by weight for both thesolution (a) and the solution (b).

Furthermore, in those cases where the solution (a) is used, there are noparticular restrictions on the quantity of the catalyst capable ofinteracting with the metal-based surfactant, provided the catalyst doesnot effect the physical properties of the formed monomolecular organicthin film, and a typical oxide-equivalent quantity is within a rangefrom 0.001 to 1 mol, and preferably from 0.001 to 0.2 mots of thecatalyst per 1 mol of the metal-based surfactant.

A method for producing an organic thin film according to the presentinvention involves a step of bringing a substrate into contact with thesolution (a) or the solution (b) (hereafter, these two options arereferred to jointly using the expression “organic solvent solution”),wherein the water content within the solution is either set ormaintained within a predetermined range. By controlling the watercontent within the organic solvent solution within a certain range, adense organic thin film is able to be formed rapidly on substratesformed from all manner of materials.

The water content within the organic solvent solution is determined onthe basis of factors such as the substrate used, and the nature of themetal-based surfactant, the catalyst, and the organic solvent.Specifically, the content must be less than that which causes problemssuch as inhibition of chemical adsorption to the substrate surface,inability to produce a dense monomolecular film, a large loss in thequantity of the metal-based surfactant used, or deactivation of thecatalyst, but must be large enough to enable adequate acceleration andactivation of the film formation.

In those cases where the substrate is brought into contact with thesolution using a dipping method, a quantity of water that is largeenough to enable adequate acceleration and activation of the filmformation refers to a quantity that enables the formation of a dense anduniform organic thin film across the entire surface of the substrate viaa single dipping operation with a contact time of no more than 10minutes, and preferably no more than 5 minutes. Specifically, a quantityof at least 50 ppm is preferred, a quantity within a range from 50 ppmto the saturated water content for the organic solvent, or morespecifically from 50 to 1000 ppm is even more preferred, and a quantitywithin a range from 200 to 800 ppm is the most desirable. Provided thewater content is 50 ppm or greater, formation of the organic thin filmcan be conducted rapidly, and provided the water content is no more than1000 ppm, the problem of deactivation of the metal-based surfactant andthe like does not arise.

The water content here refers to a measured value, obtained by a KarlFischer method, for a solution aliquot sampled from the organic solventsolution, and there are no particular restrictions on the measurementapparatus, provided it uses this type of measurement method. In thosecases where the organic solvent solution is homogenous, a solutionaliquot is sampled from the homogenous solution and measured, in thosecases where the organic solvent layer and the water layer form twoseparate layers, an aliquot is sampled from the organic solvent layerand measured, and in those cases where the water layer is dispersedwithin the organic solvent and is unable to be separated, an aliquot issampled from the dispersion and measured.

There are no particular restrictions on the method for preparing theorganic solvent solution containing the metal-based surfactant, thecatalyst such as a metal oxide that is capable of interacting with themetal-based surfactant, and water, and specific examples include thefollowing:

(1) a method in which water is added to an organic solvent solutioncontaining the metal-based surfactant and the catalyst capable ofinteracting with the metal-based surfactant, and(2) a method in which the metal-based surfactant and the catalystcapable of interacting with the metal-based surfactant are added to anorganic solvent solution containing the metal-based surfactant andwater.

Furthermore, in order to suppress any rapid reaction, the added water inthe method (1), and the added catalyst in the method (2), are preferablydiluted with an organic solvent or the like prior to addition.

There are no particular restrictions on the quantity of the catalystcapable of interacting with the metal-based surfactant in those easeswhere the catalyst is a metal oxide, metal hydroxide, metal alkoxide,chelated or coordinated metal compound, partial hydrolysis product of ametal alkoxide, or a hydrolysis product obtained by treating a metalalkoxide with a two-fold or greater equivalence of water, provided thecatalyst has no effect on the physical properties of the formedmonomolecular organic thin film, but the use of a catalyst quantity thatis typically within a range from 0.001 to 1 mol, and preferably from0.001 to 0.2 mols, or an oxide-equivalent quantity that is typicallywithin a range from 0.001 to 1 mol, and preferably from 0.001 to 0.2mols, per 1 mol of the metal-based surfactant is preferred.

Furthermore, in those cases where the catalyst capable of interactingwith the metal-based surfactant is an organic acid, the quantity of thecatalyst is typically within a range from 0.001 to 100 mols, andpreferably from 0.001 to 10 mols, per 1 mol of the metal-basedsurfactant. By using a quantity of the catalyst capable of interactingwith the metal-based surfactant that falls within this range, a densemonomolecular organic thin film with no impurities can be formedrapidly.

An organic thin film forming solution of the present invention can beobtained by stirring the mixture of the aforementioned metal-basedsurfactant, organic solvent, and the catalyst capable of interactingwith the metal-based surfactant. The stirring temperature is typicallywithin a range from −100° C. to +100° C., and is preferably from −20° C.to +50° C. The stirring time is typically within a range from severalminutes to several hours. Furthermore, in this case, ultrasoundtreatment is preferably used to enable a uniform organic thin filmforming solution to be obtained.

In some cases, a precipitate containing metal oxide or the like maydevelop in the prepared organic thin film fanning solution, andimpurities such as these precipitated substances are preferably removedat this point to ensure a dense monomolecular organic thin film with noimpurities. Precipitates can be removed easily by an operation such asfiltration or decantation.

In the present invention, during the step of bringing the substrate intocontact with the above solution, the water content within the organicsolvent solution is maintained within a predetermined range, and thesame solution is preferably used to conduct two or more repetitions ofthe contact step.

The expression “predetermined range” refers to the same predeterminedrange for the water content described above, and by maintaining thewater content within that range, a dense and uniform organic thin filmcan be formed even when a plurality of repetitions of the contact stepare conducted without changing the solution. By using the same solutionand conducting a single contact step for two or more substrates, denseand uniform organic thin films can be formed across the entire contactsurface in a comparatively short contact time.

The expression, “the same solution” excludes those cases where followinga single repetition of the contact step, either all, or a portion of thesolution is discarded and replaced with fresh solution, but as describedbelow, includes those cases where some form of method is used tomaintain the water content of the solution within the predeterminedrange.

Specific examples of methods for setting or maintaining the watercontent within the predetermined range include the following:

(1) a method in which a water layer is provided that contacts theorganic solvent solution,(2) a method in which a water-retentive material in a hydrated state isincorporated within the organic solvent solution,(3) a method in which a gas containing moisture is brought into contactwith the organic solvent solution, and(4) a method in which water is added appropriately.

These methods can be used either alone, or in combinations of two ormore different methods.

There are no particular restrictions on the water used, provided it isneutral, although the use of pure water or distilled water is preferred.Furthermore, the organic solvent may be either anhydrous, or may alreadycontain a certain quantity of water.

In the method (1) described above, in those cases where an organicsolvent is used that separates from the water layer, such as ahydrocarbon-based solvent, the water layer may either coexist in aseparated state from the organic solvent layer, or the organic solventmay be circulated or fed through the water layer before forming aseparate organic solvent layer.

In those cases where an organic solvent such as a lower alcohol is used,which does not separate from water but rather exhibits a high solubilityfor water, a method can be used in which the organic solvent solutionand the water layer are brought into contact via a membrane or the likethat is permeable to water but impermeable to the organic solvent.

In the method (2) described above, the water-retentive material ispreferably a material that does not cause the water to separate outwithin the organic solvent solution, and does not float within theorganic solvent solution.

Specific examples of suitable materials include organic-basedwater-retentive materials such as water-absorbing polymers; inorganicwater-retentive materials such as zeolites, clay silicates,vermiculites, and porous ceramics; as well as compounds such assurfactants that are capable of forming micelle molecules around a waternucleus within a solution, and of these, glass fiber filters areparticularly desirable for the reason that contamination by dirt andimpurities can be avoided.

Furthermore, compounds capable of forming micelle molecules around awater nucleus within a solution, and more specifically surfactants andthe like, can be used as the water-retentive material, and thesematerials preferably coexist within the solution in a hydrated state.

Furthermore, a method in which a hydrophilic solvent is used to improvethe solubility of water in the organic solvent is also possible. Thehydrophilic solvent used in such a case can be incorporated as amaterial capable of retaining water.

There are no particular restrictions on the quantity of waterincorporated within the water-retentive material, although a quantity ofwater that does not cause the water to separate from the water-retentivematerial in the organic solvent solution is preferred. Furthermore,water can simply be added and incorporated within a material capable ofretaining the water. Furthermore, by providing the water-retentivematerial either at the interface between the solution and the externalatmosphere, or in continuous arrangement from the external atmospherethrough into the solution, the water content within the solution can bereplenished by absorbing moisture from the humidity within the externalatmosphere.

In the method (3) described above, there are no particular restrictionson the gas used, provided it has no effect on the components within thesolution, and examples of suitable gases include air, nitrogen gas, andargon gas.

Examples of suitable methods for obtaining a gas containing moistureinclude methods in which moisture is incorporated within the gas, andmethods in which the gas is humidified.

Examples of methods for incorporating moisture within the gas includemethods in which the gas is immersed within water; methods of bringingwater and gas into contact, such as bringing the gas into contact withthe surface of water or hot water; and methods in which a gas containingwater vapor is used as is.

Examples of methods for humidifying gases include steam humidificationmethods, water injection humidification methods, and vaporizationheating methods.

Examples of methods for bringing a gas containing moisture and theorganic solvent solution into contact include methods for blowing themoisture-containing gas either into the organic solvent solution or ontothe surface of the organic solvent solution; methods in which theorganic solvent solution is left to stand, if necessary while beingstirred, in an atmosphere of the moisture-containing gas; and methods inwhich the organic solvent solution is left to stand, if necessary whilebeing stirred, in a humid atmosphere. In the methods for blowing themoisture-containing gas, a blowing apparatus, a cleaning apparatus, anda filtration apparatus and the like may also be used if required.

Furthermore, specific examples of the method (4) described above includemethods in which decreases in the water content within the organicsolvent solution are observed, and an equivalent quantity of eitherwater, or water that has been diluted with a co-soluble organic solventor the same organic solvent as the organic solvent solution is thenadded; and methods in which an organic solvent solution containing acertain quantity of water is supplied to the solution.

There are no particular restrictions on the substrate used in the methodfor producing an organic thin film according to the present invention,although substrates with surfaces that include functional groups capableof interacting with the molecules in the organic solvent solution thatform the organic thin film are preferred, and substrates that includeactive hydrogen at the surface are particularly desirable. By using asubstrate that includes active hydrogen at the surface, the activehydrogen at the substrate surface and the molecules within the organicsolvent solution can undergo a chemical interaction, thereby enablingready formation of a chemically adsorbed film on the substrate surface.

An active hydrogen refers to a hydrogen that readily dissociates as aproton, and examples of functional groups containing an active hydrogeninclude hydroxyl groups (—OH), carboxyl groups (—COOH), formyl groups(—CHO), imino groups (═NH), amino groups (—NH₂), and thiol groups (—SH).Of these, hydroxyl groups are preferred.

Specific examples of substrates that have hydroxyl groups on thesubstrate surface include metals such as aluminum, copper, and stainlesssteel, glass, silicon wafers, ceramics, plastics, paper, natural andsynthetic fibers, leather, and other hydrophilic materials. Of these,substrates formed from metals, glass, silicon wafers, ceramics, andplastics are preferred.

In the case of substrates formed from materials such as plastics orsynthetic fibers that do not have hydroxyl groups at the surface,hydrophilic groups can be introduced by pretreating the surface of thesubstrate in a plasma atmosphere containing oxygen (for example for 20minutes at 100 W), or by subjecting the substrate surface to coronatreatment. Substrates formed from polyamide resins or polyurethane resinor the like have imino groups at the surface, and the active hydrogenatoms of these imino groups, and the alkoxysilyl groups or the like ofthe metal-based surfactant can undergo a dealcoholization reaction,thereby forming siloxane linkages (—SiO—), meaning the substrates do notrequire any particular surface treatment.

Furthermore, in those cases where a substrate that has no activehydrogen atoms at the surface is used, the surface of the substrate canfirst be brought into contact with at least one compound selected from agroup consisting of SiCl₄, SiHCl₃, SiH₂Cl₂, and Cl—(SiCl₂O)_(b)—SiCl₃(wherein, b represents a natural number), and a dehydrochlorinationreaction then conducted, thus forming a silica base layer containingactive hydrogen atoms on the surface of the substrate.

There are no particular restrictions on the method used for bringing theorganic solvent solution into contact with the substrate, andconventional methods can be used. Specific examples of suitable methodsinclude dipping methods, spin coating methods, spray methods, rollercoating methods, Meyer bar methods, screen printing methods, and brushcoating methods, and of these, dipping methods are preferred.

The step of bringing the organic solvent solution into contact with thesubstrate may involve a single contact for a longer period, or aplurality of repetitions of a shorter contact period. Ultrasound mayalso be used to promote film formation.

There are no particular restrictions on the temperature at which thecontact occurs, provided the temperature is within a range that enablesthe stability of the solution to be maintained, although typically, thetemperature is within a range from room temperature to the refluxtemperature of the solvent used in preparing the solution. In order toensure a favorable temperature for the contact, the solution may eitherbe heated, or the substrate itself may be heated.

The step of bringing the substrate into contact with the organic solventsolution is preferably a step in which the substrate is immersed(dipped) in the organic solvent solution. Specific examples of methodsof immersing the substrate while maintaining the water content withinthe organic solvent solution include the following:

(a) a method which provides a water content adjustment tank and asubstrate immersion tank, wherein the solution for which the watercontent has been adjusted in the water content adjustment tank iscirculated through the substrate immersion tank,(b) a method which provides a plurality of substrate immersion tanks,wherein while the substrate is being immersed in one of the substrateimmersion tanks, the water content within the other substrate immersiontank or tanks is adjusted, and(c) a method in which a device for maintaining the aforementioned watercontent within a predetermined range is provided in direct contact withthe substrate immersion tank, thereby enabling appropriate replenishingof the water content.

A step (B) of washing the substrate surface may be provided followingcompletion of the step of bringing the substrate into contact with theorganic solvent solution, for the purpose of removing excess reagents orimpurities adhered to the substrate surface. By providing a washingstep, the film thickness can be controlled.

There are no particular restrictions on the washing method employed,provided the method is capable of removing adherends from the substratesurface, and specific examples of suitable methods include methods inwhich the substrate is immersed in a solvent capable of dissolving themetal-based surfactant; methods in which the substrate is allowed tostand, either under vacuum or in a normal pressure atmosphere, to allowevaporation to proceed, and methods in which an inert gas such as drynitrogen gas is used to blow any residue off the substrate surface.

Furthermore, a step (C) of heating the substrate may also be providedfollowing the step of bringing the substrate into contact with theorganic solvent solution, for the purpose of stabilizing the film formedon the surface of the substrate. This step (C) of heating the substrateis preferably provided after the aforementioned washing step (B). Theheating temperature can be selected in accordance with factors such asthe stability of the substrate and the film.

In the present invention, the step of bringing the substrate intocontact with the organic solvent solution is preferably conducted in aspace that is maintained at a humidity of at least 40% RH, andconducting the step within a space that is maintained at a humidity ofat least 60% RH is even more desirable. In this type of space, the watercontent within the organic solvent solution can be maintained morefavorably, meaning even if substrates are continuously brought intocontact with the solution, dense monomolecular films can still be formedwith good reproducibility.

The method for producing an organic thin film according to the presentinvention can be used either for the production of a monomolecular film,or for the production of a multilayer film of two or more layers, but isparticularly suited to the production of monomolecular films.Furthermore, this method can also be used as a method of forming a filmon a surface by physical adsorption.

An example of a suitable method for storing the solution used in themethod for producing an organic thin film according to the presentinvention involves treating the organic solvent solution containingeither (α) a metal-based surfactant having at least one hydrolyzablegroup, and a catalyst capable of interacting with the metal-basedsurfactant, or (β) a metal-based surfactant having at least one hydroxylgroup, with water, thereby setting the water content within the organicsolvent solution to a value within a predetermined range, and thenmaintaining the water content within the organic solvent solution withinthat predetermined range while the solution is sealed inside a vessel.Examples of suitable methods for setting the water content within theorganic solvent solution to a value within a predetermined range, andthen maintaining the water content within the organic solvent solutionwithin that predetermined range include the same methods as thosedescribed above.

Sealing the solution inside a vessel prevents any volatilization of thewater content, together with the organic solvent, on contact with theatmosphere. The water content within the organic thin film-formingsolution of the present invention effects the organic thin film formingability of the solution, and consequently the water content within thesolution is preferably maintained within a predetermined range, evenduring storage.

By using the method for producing an organic thin film described above,monomolecular films, self-assembly films, chemically adsorbed films, andfilms combining all of these properties can be obtained.

2) Self-Assembly Film forming Solution

In a self-assembly film forming solution of the present invention, themolecules for forming the self-assembly film form an aggregate withinthe solution.

In an organic solvent solution in which the water content is set withina predetermined range (hereafter referred to as the “organic thin filmforming solution”), in those cases where the molecules for forming theorganic thin film form an aggregate within the solution, the resultingorganic thin film is a self-assembly film (and in these cases, theorganic thin film forming solution is called a “self-assembly filmforming solution”).

In the aforementioned formula (IV), with the exception that the group X¹represents a hydroxyl group or a hydrolyzable group, R¹¹, M¹, n₁, and m₁have the same meanings as R¹, M, n, and m respectively within theaforementioned formula (I).

Furthermore, in the aforementioned formula (V), with the exception thatthe group X² represents a hydroxyl group or a hydrolyzable group, R²¹,R³¹, R⁴¹, M², Y², p₁, q₁, m₂, and r₂ have the same meanings as R², R³,R⁴, M, Y, p, q, m, and r respectively within the aforementioned formula(II).

Specific examples of the compounds represented by the formula (IV) orthe formula (V) include those compounds listed in relation to theaforementioned formula (I) and formula (II).

X¹ and X² need not necessarily include hydrolyzable groups, and hydroxylgroup-containing compounds such as those represented by theaforementioned formula (III) are also suitable.

In the present invention, a self-assembly film refers to a film thatforms with a regular structure without any external compelling forces.In a self-assembly film forming solution, the molecules of themetal-based surfactant are not solvated by the solvent, meaning thatrather than existing in isolation, they group together, forming anaggregate.

In those cases where a metal-based surfactant having at least onehydrolyzable group is used as the metal-based surfactant, the aggregateis obtained through treatment of the metal-based surfactant with thecatalyst capable of interacting with the metal-based surfactant, andwater, whereas in those cases where a metal-based surfactant having atleast one hydroxyl group is used as the metal-based surfactant, theaggregate is obtained through treatment of the metal-based surfactantwith water.

Examples of suitable configurations for the aggregate includeconfigurations in which the molecules are aggregated together viaintermolecular forces, coordination bonding, or hydrogen bonding betweenhydrophobic portions or hydrophilic portions within the molecules;configurations in which the molecules that form the film are bondedtogether via covalent bonds; configurations in which micelles or thelike are formed either around, or via, another medium such as water thatacts as a nucleus or an mediate; and configurations that employ acombination of the above.

There are no particular restrictions on the shape of the aggregate, andspherical, chain-like, or band-like shapes are all suitable. There areno particular restrictions on the average particle diameter of theaggregate, although diameters within a range from 10 to 1,000 nm arepreferred.

Furthermore, the value of the zeta potential (the interfaceelectrokinetic voltage) of the aggregate is preferably greater than thezeta potential of the substrate within the same solution. Cases in whichthe zeta potential of the aggregate is positive and the zeta potentialof the substrate is negative are particularly desirable. By using aself-assembly film forming solution that forms an aggregate with thistype of zeta potential, a dense monomolecular film that exhibitscrystallinity can be produced.

3) Chemically Adsorbed Film

A chemically adsorbed film of the present invention is a chemicallyadsorbed film formed on top of a substrate, wherein the substrate is notcrystalline, and the chemically adsorbed film is crystalline. In otherwords, the film is crystalline regardless of whether or not thesubstrate exhibits crystallinity. In this case, the term “crystalline”includes both polycrystals and single crystals.

4) Method for Producing Monomolecular Film

A method for producing a monomolecular film according to the presentinvention is a method that includes a step in which a solutioncontaining a metal-based surfactant is applied to the surface of asubstrate using at least one method selected from a group consisting ofdipping methods, spin coating methods, roll coating methods, Meyer barmethods, screen printing methods, offset printing methods, brush coatingmethods, and spray methods, and in that step, a solution containing ametal-based surfactant having a hydrocarbonoxy group or acyloxy group asa hydrolyzable group is dripped onto the substrate, and pressure is thenapplied from above the dripped solution to spread the solution acrossthe substrate. There are no particular restrictions on the quantity ofsolution dripped onto the substrate, or the location in which thesolution is dripped, and these factors can be selected in accordancewith the desired location and surface area for the monomolecular film tobe formed.

There are no particular restrictions on the method used for applyingpressure from above the dripped solution, provided the method enablesthe dripped solution to be spread across the surface of the substrate,and specific examples of suitable methods include methods in which afilm, a sheet, or a flat plate is laid on top of the substrate surfaceand pressure is then applied using a roller.

The solvent solution containing the metal-based surfactant preferablyalso contains a catalyst capable of activating the hydrolyzable group ofthe metal-based surfactant.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows thin-film X-ray crystal diffraction diagrams for organicthin films SAM-25 to SAM-27.

FIG. 2 shows SPM charts during a process for forming SAM-27, wherein thecharts represent the organic thin film obtained after immersion times of(a) less than 1 second, (b) 15 seconds, (c) 30 seconds, and (d) 1minute.

FIG. 3 shows SPM charts during a process for forming SAM-31, wherein thecharts represent the organic thin film obtained after immersion times of(a) less than 1 second, (b) 15 seconds, (c) 1 minute, and (d) 5 minutes.

BEST MODE FOR CARRYING OUT THE INVENTION

As follows is a more detailed description of the present invention usinga series of examples, although the scope of the present invention is inno way restricted by the following examples.

Example 1 (1) Catalyst Preparation-1

12.4 g of titanium tetraisopropoxide (A-1, purity: 99%, titaniumoxide-equivalent concentration: 28.2% by weight, manufactured by NipponSoda Co., Ltd.) was dissolved in 45.0 g of toluene in a four neck flask,and following replacement of the air inside the flask with nitrogen gas,the temperature was cooled to −80° C. in an ethanol/liquid nitrogenbath. In a separate vessel, 1.26 g of ion exchange water (H₂O/Ti=1.6(molar ratio)) was mixed with 11.3 g of isopropanol, cooled to atemperature of −80 to −70° C., and then added dropwise to the above fourneck flask with constant stirring. During the dropwise addition, theliquid temperature inside the flask was maintained at −80 to −70° C.Following completion of the dropwise addition, the resulting mixture wasstirred for 30 minutes under continued cooling, and the temperature wasthen raised to room temperature with constant stirring, yielding acolorless and transparent partially hydrolyzed solution (C-1) with atitanium oxide-equivalent concentration of 5% by weight.

(2) Catalyst Preparation-2

In a four neck flask in which the air had been replaced with nitrogengas, 530 g of titanium tetraisopropoxide (A-1, purity: 99%, titaniumoxide-equivalent concentration: 28.2% by weight, manufactured by NipponSoda Co., Ltd.) was dissolved in 1960 g of toluene, and the temperaturewas cooled to −15° C. in an ethanol/dry ice bath. In a separate vessel,30.4 g of ion exchange water (molar ration (H₂O/Ti)=0.9) was mixed with274 g of isopropanol, and then added dropwise to the above four neckflask with constant stirring over a 90 minute period. During thedropwise addition, the liquid temperature inside the flask wasmaintained at −15 to −10° C. Following completion of the dropwiseaddition, the resulting mixture was stirred for 30 minutes at −10° C.,the temperature was raised to room temperature, and the stirring wascontinued for a further 1 hour, yielding a colorless, transparentsolution. This solution was cooled to −80° C. in an ethanol/dry icebath, and a mixed solution of 20.3 g of ion exchange water (H₂O/Ti)=0.6)and 183 g of isopropanol was added dropwise with constant stirring overa 90 minute period. Following completion of the dropwise addition, thetemperature was slowly returned to room temperature over a three hourperiod, and the solution was then refluxed for two hours at atemperature of 90 to 100° C., yielding a colorless and transparentpartially hydrolyzed solution (C-2) with a titanium oxide-equivalentconcentration of 5% by weight. This solution was a sharp monodispersedsol with an average particle diameter of 5.6 nm.

(3) Catalyst Preparation-3

17.79 g (62.6 mmol) of titanium tetraisopropoxide (A-1, purity: 99%,titanium oxide-equivalent concentration: 28% by weight, manufactured byNippon Soda Co., Ltd.) and 65.31 g of anhydrous toluene were mixedtogether in flask under a nitrogen gas atmosphere at a liquidtemperature of 18° C., yielding a solution. A mixture of 1.69 g of water(93.9 mmol, H₂O/Ti=1.5 (molar ratio)), 30.42 g of anhydrous isopropanol,and 30.42 g of anhydrous toluene (the water concentration was equivalentto the 22% that represents the saturated solubility of water in anisopropanol-toluene mixed solvent), was then added to the solution in adropwise manner with constant stirring over two hours, with the liquidtemperature maintained at 18 to 20° C., thus yielding a pale yellow,transparent solution. When the solution was then stirred for a further1.5 hours at 18° C., the yellow color darkened slightly, but when thesolution was then refluxed for 2.5 hours, a colorless, transparentsolution was obtained. The oxide concentration of the solution was 3.4%by weight. Toluene was then added to this solution to dilute the oxideconcentration to 1.0% by weight, thus completing preparation of acatalyst (C-3).

(4) Catalyst Preparation-4

A silica sol dispersed in isopropanol (IPA) (IPA-ST-S, 25% by weight,manufactured by Nissan Chemical Industries, Ltd.) was dispersed inanhydrous toluene, thus yielding a dispersion (C-4) with a silicaequivalent concentration of 1% by weight.

(5) Catalyst Preparation-5

12.4 g of titanium tetraisopropoxide (A-1, purity: 99%, titaniumoxide-equivalent concentration: 28.2% by weight, manufactured by NipponSoda Co., Ltd.) was dissolved in 45.0 g of toluene in a four neck flask,and following replacement of the air inside the flask with nitrogen gas,the temperature was cooled to −20° C. in an ethanol/dry ice bath. In aseparate vessel, 1.26 g of ion exchange water (H₂O/Ti=1.6 (molar ratio))was mixed with 11.3 g of isopropanol, cooled to a temperature of −20°C., and then added dropwise to the above four neck flask with constantstirring. During the dropwise addition, the liquid temperature insidethe flask was maintained at −20° C. Following completion of the dropwiseaddition, the resulting mixture was stirred for 30 minutes undercontinued cooling, and the temperature was then raised to roomtemperature with constant stirring, yielding a colorless and transparentpartially hydrolyzed solution (C-5) with a titanium oxide-equivalentconcentration of 5% by weight.

(6) Catalyst Preparation-6

Tetrakis(trimethylsiloxy)titanium (manufactured by Gelest Inc.) wasdissolved in anhydrous toluene, yielding a catalyst solution (C-6) witha concentration of 1% by weight.

(7) Catalyst Preparation-7

With the exception of adding the ion exchange water dropwise at −40° C.,a partially hydrolyzed solution (C-7) was prepared in the same manner asthe catalyst preparation-1.

(8) Metal-Based Surfactant-1

The material M-1 described below was used as the metal-based surfactantfor preparing an organic thin film forming solution.

M-1: n-octadecyltrimethoxysilane (ODS), manufactured by Gelest Inc.

(9) Metal-Based Surfactant-2

Using the method described below, M-2: n-octadecyltrihydroxysilane(ODHS) was prepared as the metal-based surfactant for preparing anorganic thin film forming solution.

A four neck flask in which the air had been replaced with nitrogen gaswas charged with 82 g of anhydrous ethanol, 0.6 g of 0.1N hydrochloricacid, and 9 g of water, and the mixture was cooled to 0° C.Subsequently, with the mixture inside the flask undergoing constantstirring, 7.8 g of octadecyltriethoxysilane was added dropwise.Following completion of this dropwise addition, the reaction mixture washeld at room temperature for three hours. The reaction liquid was thenfiltered off, and the solid was dried under vacuum at room temperaturefor two hours, yielding 4.4 g of a white powder (M-2) (yield: 72%).

(10) Organic Thin Film Forming Solution Preparation Method-1

Ion exchange water was added to anhydrous toluene and stirred briskly,yielding the hydrous toluene shown in Table 1. The metal-basedsurfactant M-1 was added to this hydrous toluene in sufficient quantityto yield a final concentration of 0.5% by weight, and the mixture wasstirred at room temperature for 30 minutes. Subsequently, one of thecatalysts C-1 to C-4 was added dropwise to the solution in thepredetermined quantity shown in Table 1, and following completion of thedropwise addition, the mixture was stirred at room temperature for threehours, yielding a solution (SA-1 through SA-10).

(11) Organic Thin Film Forming Solution Preparation Method-2

The metal-based surfactant M-1 was added to hydrous toluene with a watercontent of 350 ppm, in sufficient quantity to yield a finalconcentration of 0.5% by weight, and the mixture was then stirred atroom temperature for 30 minutes. Subsequently, one of the catalysts C-1to C-4 was added dropwise to the solution in a predetermined quantity,and following completion of the dropwise addition, the mixture wasstirred at room temperature for three hours. A 100 g sample of each ofthe thus formed solutions was transferred to a bottle, a glass fiberfilter paper of diameter 3 cm (GA-100, manufactured by Toyo Roshi Co.,Ltd.) that had been thoroughly wet with water was immersed at the bottomof the bottle, and the bottle was sealed. The bottle was then allowed tostand at room temperature for two hours, yielding a solution (SA-11through SA-14).

(12) Organic Thin Film Forming Solution Preparation Method-3

The metal-based surfactant M-1 was added to hydrous toluene with a watercontent of 350 ppm, in sufficient quantity to yield a finalconcentration of 0.5% by weight, and the mixture was then stirred atroom temperature for 30 minutes. Subsequently, one of the catalysts C-1to C-7 was added dropwise to the solution in a predetermined quantity,and following completion of the dropwise addition, the mixture wasstirred at room temperature for three hours. A 100 g sample of each ofthe thus formed solutions was transferred to a bottle, and using an 18L/minute blower and a Kinoshita glass ball filter, saturated water vaporwas bubbled through the solution at 25° C., yielding a solution (SA-15through SA-18, SA-22 through SA-25) with an adjusted moisture content.

(13) Organic Thin Film Forming Solution Preparation Method-4

Ion exchange water was added to anhydrous toluene and stirred briskly,yielding a hydrous toluene with a water content of 100 ppm. Themetal-based surfactant M-1 was added to this hydrous toluene insufficient quantity to yield a final concentration of 0.5% by weight,and the mixture was stirred at room temperature for 30 minutes.Subsequently, the catalyst C-3 was added dropwise to the solution in thepredetermined quantity shown in Table 1, and following completion of thedropwise addition, the mixture was stirred at room temperature for threehours. A 100 g sample of each of the thus formed solutions wastransferred to a bottle, 10 g of ion exchange water was added, thebottle was sealed, and the mixture was then agitated for 5 minutes at25° C., gently enough to avoid emulsification, thus yielding a solutionwith a saturated water content (SA-19 and SA-20). Following agitation,the water separated and formed a water layer.

(14) Organic Thin Film Forming Solution Preparation Method-5

Using the method described above in the organic thin film formingsolution preparation method-3 (and using the catalyst C-3), toluene withan unknown water content was used, and by adjusting the bubbling time, asolution with a water content of 250 ppm (SA-21) was obtained.

(15) Organic Thin Film Forming Solution Preparation Method-6

The metal-based surfactant M-2 was added to tetrahydrofuran (THF) with awater content of 400 ppm, in sufficient quantity to yield a finalconcentration of 0.5% by weight, and the mixture was then stirred atroom temperature for three hours. A 100 g sample of the thus formedsolution was transferred to a bottle, a glass fiber filter paper ofdiameter 3 cm (GA-100, manufactured by Toyo Roshi Co., Ltd.) that hadbeen thoroughly wet with water was immersed at the bottom of the bottle,and the bottle was sealed. The bottle was then allowed to stand at roomtemperature for two hours, yielding a solution (SA-26).

(16) Organic Thin Film Forming Solution Preparation Method-7

Comparative organic thin film forming solutions (R-1 through R-6) wereprepared in the manner described below.

R-1: With the exception of not adding the ion exchange water, a solutionwas prepared in the same manner as the organic thin film formingsolution preparation method-1.R-2 to R-4: Ion exchange water was added to anhydrous toluene andstirred briskly, yielding hydrous toluene with a water content of 100,210, and 94 ppm respectively. The metal-based surfactant M-1 was thenadded to the solution in sufficient quantity to yield a finalconcentration of 0.5% by weight, and the mixture was stirred at roomtemperature for 30 minutes. Subsequently, a predetermined quantity ofthe catalyst C-2 was added dropwise to the solution, and followingcompletion of the dropwise addition, the mixture was stirred at roomtemperature for three hours, completing the preparation.R-5: With the exception of not adding the catalyst, a solution wasprepared in the same manner as the organic thin film forming solutionpreparation method-1.R-6: The metal-based surfactant M-1 was dissolved in anhydrous toluene,and following stirring at room temperature for 30 minutes, the catalystC-5 was added dropwise, and the resulting mixture was then stirred atroom temperature for three hours to complete the preparation.

(17) Evaluation of Organic Thin Film Forming Solutions

The water content within each solvent or solution, the average particlediameter, and the zeta potential were measured using the methodsdescribed below. The results are summarized in Table 1.

In Table 1, the value for the water content prior to treatment refers tothe water content within the toluene for SA-1 to SA-10, and R-1 to R-6,to the water content of the solution prior to insertion of the glassfiber filter paper for SA-11 to SA-14, to the water content within thesolution prior to bubbling for SA-15 to SA-18, and SA-22 to SA-25, andto the water content within the solution prior to addition of the waterfor SA-19 and SA-20.

<Water Content>

The water content was measured using a Karl Fischer moisture meter(CA-07, manufactured by Dia Instruments Co., Ltd.) using a coulometrictitration method.

<Average Particle Diameter>

The average particle diameter was measured using a dynamic lightscattering particle diameter measurement apparatus (HPPS, manufacturedby Malvern Instruments Ltd.).

<Zeta Potential>

The zeta potential was measured using a laser zeta potential meter(ELS-8000, manufactured by Otsuka Electronics Co., Ltd.).

TABLE 1 Water content Average particle Organic thin Mixing ratio * priorto Water content diameter of film forming Catalyst between M-1 treatmentwithin solution particles within Zeta solution (C) and C (ppm) (ppm)solution potential SA-1 C-1 95:5 1000 520 — — SA-2 C-1 90:10 800 480 — —SA-3 C-2 99:1 700 510 — — SA-4 C-2 90:10 1000 485 — — SA-5 C-2 60:401000 380 — — SA-6 C-3 95:5 800 450 — — SA-7 C-3 90:10 1000 480 — — SA-8C-4 90:10 1000 390 — — SA-9 C-2 90:10 450 140 — — SA-10 C-2 90:10 320107 — — SA-11 C-1 90:10 145 550 — — SA-12 C-2 90:10 150 560 — — SA-13C-3 90:10 132 580 — — SA-14 C-4 90:10 110 560 — — SA-15 C-1 90:10 145570 — — SA-16 C-2 90:10 150 580 — — SA-17 C-3 90:10 132 580 — — SA-18C-4 90:10 110 570 — — SA-19 C-3 95:5 110 540 — — SA-20 C-3 90:10 110 530— — SA-21 C-3 90:10 — 250 — — SA-22 C-7 90:10 240 467 — — SA-23 C-590:10 250 520 42 nm +47 mV SA-24 C-5 50:50 220 490 23 nm +53 mV SA-25C-6 98:2 230 510 150 nm  +116 mV  SA-26 — — — 410 — — R-1 C-2 90:10 7 12— — R-2 C-2 90:10 100 35 — — R-3 C-2 90:10 210 82 — — R-4 C-2 90:10 9440 — — R-5 — — 350 510 Measurement  0 mV impossible R-6 C-5 90:10 3 2Measurement  0 mV impossible * (number of mols of M-1): (metaloxide-equivalent number of mols of metal component within C solution)

From Table 1 it is evident that in the solutions SA-1 through SA-10, thewater content within the toluene decreases to approximately half of theinitial value on preparation of the organic thin film forming solution.The reason for this decrease remains unclear, but it may representadhesion to the walls of the vessel or volatilization into theatmosphere.

From the results for the solutions SA-11 to SA-21 it is clear that byusing a method in which water is added after solution preparation, amethod in which a water-soaked glass fiber filter paper is placed in thesolution, or a method in which water vapor is blown through thesolution, the water content within the solution can be increased. Thisfinding suggests that even for an organic thin film forming solution inwhich the water content has fallen for some reason, a water content thatexceeds a predetermined quantity can be obtained by employing a devicefor maintaining the water content, and consequently even in those caseswhere a solution that has been stored is used, the stored solution canbe used as the organic thin film forming solution without having toreadjust the water content within the solution.

From the results for SA-23 through SA-25 in Table 1 it is clear thatwhereas the external appearance of the prepared solution is transparent,particles have been formed within the solution. Furthermore, theseparticles are formed by addition of the water and the catalyst. Fromthese results it is inferred that the metal-based surfactant M-1 isundergoing some form of interaction with the water and the catalyst,thereby forming an aggregate.

These prepared solutions displayed positive zeta potentials. When thezeta potential value for possible substrates including soda lime glass,alkali-free glass substrates, and a silicon wafer was measured in thesame solutions, the results were −42 mV, −69 mV, and −35 mVrespectively, smaller values than the zeta potential of the solution ineach case. The zeta potential of the solution in the case where waterand the catalyst were not added was 0 mV.

(18) Organic Thin Film Formation-1

Soda lime glass substrates (SLG), alkali-free glass substrates (AN100,manufactured by Asahi Glass Co., Ltd.), silicon wafers (Si), andstainless steel substrates (SUS316, SUS304) that had been subjected toultrasound cleaning and ozone cleaning were immersed in theaforementioned solutions (SA-1 through SA-26, and R-1 through R-6) forthe predetermined time periods shown in Table 2, subsequently removedfrom the solutions, subjected to ultrasound cleaning in toluene, andthen dried at 60° C. for 10 minutes, thereby forming organic thin filmsof M-1 (SAM-1 to SAM-31, and RL-1 to RL-6) and organic thin films of M-2(SAM-32).

(19) Evaluation of Organic Thin Films

Measurement of the contact angle, evaluation of the film adhesiveness,measurement of the film thickness, XPS analysis, SPM analysis, andmeasurement of the film crystallinity for each of the obtained organicthin films were conducted using the methods described below. The resultsof the contact angle, film adhesiveness, and film thickness measurementsare summarized in Table 2.

<Contact Angle>

The contact angle was measured by using a microsyringe to drip 5 μl ofwater, toluene, or tetradecane onto the surface of each sample, waitingfor 60 seconds, and then measuring the contact angle using a contactangle measurement device (360S, manufactured by Erma Inc.)

<Film Adhesiveness>

The organic thin film was subjected to ultrasound cleaning for one hourin water, and the contact angle was then remeasured and compared withthe value obtained prior to ultrasound cleaning. If the values were thesame, the film was recorded using the symbol O, whereas if the value hadfallen, the film was recorded using the symbol x.

<Film Thickness>

The film thickness of each of the obtained organic thin films wasmeasured using a multiple angle spectroscopic ellipsometer (manufacturedby J. A. Woollam Co., Inc.).

<X-Ray Photoelectron Spectroscopic Analysis>

Analysis of the elements within each of the films was conducted using anX-ray photoelectron spectroscopy apparatus (an XPS apparatus, Quantum2000, manufactured by Ulvac-Phi Inc.).

<SPM Analysis>

The formation process for each of the obtained organic thin films, andthe presence of film defects were evaluated using a scanning probemicroscope (SPM: SPA400, manufactured by Seiko Instruments Inc.).

<Film Crystallinity>

The crystallinity of each of the obtained organic thin films wasmeasured using a thin-film X-ray diffraction apparatus (ATX-G,manufactured by Rigaku Corporation).

TABLE 2 Organic thin Immersion Film contact angle (°) Film Organic filmforming time Toluene or Film thickness thin film solution Substrate(minutes) Water tetradecane* adhesiveness (nm) Examples SAM-1 SA-1 SLG 2105 35 ∘ — SAM-2 SA-1 AN100 5 106 36 ∘ — SAM-3 SA-1 Si 10 102 33 ∘ —SAM-4 SA-2 SLG 2 106 36 ∘ — SAM-5 SA-3 AN100 5 104 34 ∘ — SAM-6 SA-4 Si10 105 32 ∘ — SAM-7 SA-5 SLG 2 100 30 ∘ — SAM-8 SA-6 AN100 2 101 32 ∘ —SAM-9 SA-7 Si 10 101 31 ∘ — SAM-10 SA-8 SLG 5 100 30 ∘ — SAM-11 SA-9 SLG5 101 31 ∘ — SAM-12 SA-10 SLG 5 99 30 ∘ — SAM-13 SA-11 SLG 1 102 32 ∘ —SAM-14 SA-12 AN100 2 106 36 ∘ — SAM-15 SA-13 Si 5 102 32 ∘ — SAM-16SA-14 SLG 5 100 30 ∘ — SAM-17 SA-15 SLG 1 103 34 ∘ — SAM-18 SA-16 Si 5104 33 ∘ — SAM-19 SA-17 AN100 2 102 32 ∘ — SAM-20 SA-18 SLG 5 100 31 ∘ —SAM-21 SA-19 Si 5 100 30 ∘ — SAM-22 SA-20 AN100 2 107 35 ∘ — SAM-23SA-22 SUS316 5 109 23 ∘ — SAM-24 SA-22 SUS304 5 110 27 ∘ — SAM-25 SA-23SLG 1 105 35 ∘ 2.5 SAM-26 SA-23 AN100 2 105 35 ∘ 2.5 SAM-27 SA-23 Si 3106 36 ∘ 2.7 SAM-28 SA-24 AN100 2 102 33 ∘ 2.5 SAM-29 SA-24 Si 2 106 36∘ 2.6 SAM-30 SA-25 AN100 3 104 34 ∘ 2.5 SAM-31 SA-25 Si 5 105 32 ∘ 2.6SAM-32 SA-26 SLG 5 102  32* ∘ — Compara- RL-1 R-1 SLG 30 82 13 x — tiveRL-2 R-2 Si 60 73  9 x — examples RL-3 R-3 SLG 5 92 26 x — RL-4 R-4 SLG5 88 19 x — RL-5 R-5 Si 30 65 13 x Measurement impossible RL-6 R-6 Si 6073  9 x Measurement impossible

From Table 2 it is evident that at water content values of no more than50 ppm, an organic thin film with a satisfactory contact angle cannot beobtained even after lengthy periods. From this finding it is clear thatin order to obtain a dense monomolecular film, (i) a water contentgreater than a predetermined quantity is required, and (ii) in thosecases where the water content is less than this predetermined quantity,water must be replenished using a water retention device, therebyforming a solution in which the water content is maintained at a levelabove the predetermined quantity.

When the films SAM-1 to SAM-24 were analyzed using XPS, a strong carbonpeak, which is not from the substrate, was observed. The fact thatcomponent elements of the substrate were also confirmed at the sametime, together with the measurement principles of the apparatus, suggestthat the film thickness was no more than 10 nanometers, and that thein-plane distribution of the carbon was uniform. The carbon content ofthe films of the comparative examples RL-1 to RL-4 was less than ⅓ thatobserved for the examples.

Furthermore, measurement of the film thickness of the films SAM-25 to 31revealed values substantially equal to the theoretical molecular lengthof the metal-based surfactant M-1 (approximately 2.3 nm), confirmingthat the films SAM-25 to 31 were monomolecular films.

In the comparative examples R-5 and R-6, measurement of the filmthickness was impossible, confirming that a monomolecular film had notbeen obtained. The above results suggest that in an organic thin filmforming solution, the generation of aggregate particles of the moleculesthat form the organic thin film, and a zeta potential for thoseparticles that is larger than the zeta potential of the substrate onwhich the organic thin film is formed, are important factors in enablinga favorable organic thin film to be produced rapidly.

Furthermore, even when the metal-based surfactant M-2 was used, afavorable organic thin film SAM-32 was still able to be formed. Thissuggests organic thin film formation that involves the silanol groups ofthe metal-based surfactant having a hydroxyl group.

X-ray diffraction diagrams for the films SAM-25 to SAM-27 are shown inFIG. 1. From FIG. 1 it is clear that the organic thin films exhibitfavorable crystallinity with an interplanar spacing of 4.1 Å. From theabove results it is evident that the molecules that constitute the filmare arrayed regularly and with a high density, confirming that acrystalline monomolecular film can be formed extremely quickly, even onan amorphous substrate such as a glass substrate.

Furthermore, in the film formation process for SAM-27 and SAM-31, theimmersion time was divided into periods, and by inspecting the substratesurface after each time period using SPM, the changes during the filmformation process were measured. The resulting SPM charts are shown inFIG. 2A, FIG. 2B, FIG. 2C, FIG. 2D, FIG. 3A, FIG. 3B, FIG. 3C, and FIG.3D respectively. FIG. 2A, FIG. 2B, FIG. 2C, and FIG. 2D shows the SPMcharts after immersion times of FIG. 2A; less than 1 second, FIG. 2B; 15seconds, FIG. 2C; 30 seconds, and FIG. 2D; 1 minute, whereas FIG. 3A,FIG. 3B, FIG. 3C, and FIG. 3D show the SPM charts after immersion timesof FIG. 3A; less than 1 second, FIG. 3B; 15 seconds, FIG. 3C; 1 minute,and FIG. 3D; 5 minutes.

From FIG. 2A, FIG. 2B, FIG. 2C, FIG. 2D, FIG. 3A, FIG. 3B, FIG. 3C, andFIG. 3D, it is evident that the organic thin film forms gradually on thesubstrate surface as the time progresses. Furthermore, FIG. 2A and FIG.3A suggest that rather than growing in single molecule steps, the filmgrows in units equivalent to a single aggregate.

When the particle diameter of those aggregates were measured off FIG. 2Aand FIG. 3A, the results were approximately 50 nm for FIG. 2A, FIG. 2B,FIG. 2C, and FIG. 2D, and approximately 200 nm for FIG. 3A, FIG. 3B,FIG. 3C, and FIG. 3D. These aggregate particle sizes show a favorablecorrelation with the particle surface areas calculated from the particlesizes observed within the organic thin film forming solution (SAM-27: 42nm, SAM-31: 150 nm).

The above findings suggest that, within the organic thin film formingsolution, the aggregates of the molecules that form the self-assemblyfilm act as the growth units for the rapid growth of the dense organicthin film.

(20) Organic Thin Film Formation-2

Under conditions including a temperature of 25° C. and a humidity of35%, 10 pieces of ozone-cleaned, rectangular, alkali-free glasssubstrates of dimensions 2 cm×5 cm were immersed simultaneously in 100 gof the solution SA-21, and following 5 minutes immersion, the substrateswere removed, subjected to ultrasound cleaning in toluene, and thendried for 10 minutes, thus yielding organic thin films. This operationwas repeated 20 times, and the water content within the solution, andthe characteristics of the produced chemically adsorbed films wereevaluated. Furthermore, saturated water vapor was then bubbled throughthe used solution to return the water content to 250 ppm, and the sameoperation was then repeated, yielding additional organic thin films. Theresults are summarized in Table 3.

TABLE 3 Immersion 1st 5th 10th 15th 20th After repetition repetitionrepetition Repetition Repetition repetition bubbling Water content 250208 156 112 101 250 (ppm) Contact angle: 107 95 92 86 83 108 water (°)Contact angle: 35 28 23 16 12 36 toluene (°)

From Table 3 it is evident that as the number of substrate immersionrepetitions is increased, the water content within the solutiondecreases, and the contact angle of the formed organic thin films falls.These results suggest that if the water content decreases, a densemonomolecular film cannot be formed in the same immersion time as thatused for cases when the water content was higher.

(21) Organic Thin Film Formation-3

(Preparation of Organic Thin Film Forming Solution)

9.0 g of titanium tetraisopropoxide (product name: A-1, purity: 99%,titanium oxide-equivalent concentration: 28.2% by weight, manufacturedby Nippon Soda Co., Ltd.) was dissolved in 91.0 g of toluene in a fourneck flask, and following replacement of the air inside the flask withnitrogen gas, the temperature was cooled to −60° C. in a modifiedalcohol/dry ice bath. In a separate vessel, 2.0 g of ion exchange water(H₂O/Ti 3.5 (molar ratio)) was mixed with 98.0 g of isopropanol, cooledto a temperature of −60 to −50° C., and then added dropwise to the abovefour neck flask with constant stirring. During the dropwise addition,the liquid temperature inside the flask was maintained at −60 to −50° C.Following completion of the dropwise addition, the resulting mixture wasstirred for 5 minutes under continued cooling, and then stirred for afurther one hour at −40° C., and the temperature was then raised to roomtemperature, yielding a colloid solution.

Subsequently, 0.65 g of the metal-based surfactant M-1 and 1.0 g of theabove colloid solution were added to 98 g of hydrous toluene (watercontent: 460 ppm) at room temperature, and the mixture was then immersedin an ultrasound bath for 30 minutes, thereby achieving dissolution andyielding an organic thin film forming solution (SA-101).

Furthermore, with the exception of adding 20 mg of titanic acid(titanium hydroxide, manufactured by Mitsuwa Chemicals Co., Ltd.)instead of the above colloid solution, preparation was conducted in thesame manner as above, and the mixture was then immersed in an ultrasoundbath for one hour, yielding a suspension. This suspension was thenfiltered to remove the insoluble components, thereby yielding an organicthin film forming solution (SA-102).

A four neck flask was charged with 99 g of water-saturated toluene(water content: 460 ppm), and 0.45 g of a 10% toluene solution oftitanium tetraisopropoxide (H₂O/Ti 16 (molar ratio)) was then addeddropwise at room temperature with continuous stirring, thereby yieldinga colloid solution.

0.65 g of the metal-based surfactant M-1 was then added to this colloidsolution at room temperature, and the mixture was then immersed in anultrasound bath for 30 minutes, thereby achieving dissolution andyielding an organic thin film forming solution (SA-103).

(Organic Thin Film Formation, Organic Thin Film Evaluation)

Three glass slides were prepared, and these were then immersed for 5minutes in the organic thin film forming solutions (SA-101 to SA-103)prepared above. The glass slides were then removed, the surfaces werewashed with toluene, and the slides were dried for 10 minutes at 60° C.,thereby yielding glass slides with an ODS organic thin film (SAM-101 toSAM-103) formed on the surfaces thereof. The thus obtained sets of threeorganic thin film glass slides were then subjected to the evaluation<contact angle measurement> described below.

A microsyringe was used to drip 5 μl of water or tetradecane onto thesurface of samples of the three organic thin film-coated glass slidesobtained above, and the slides were then left to stand for 60 seconds.Subsequently, the contact angle at the water and tetradecane dropsurface was measured using a contact angle measurement device (360S,manufactured by Erma Inc.). The results are shown in Table 4. In Table4, the units for the contact angles are degrees)(°).

TABLE 4 Organic thin film contact Organic Organic thin film angle (°)thin film forming solution Water Tetradecane SAM-101 SA-101 106.9 35.6SAM-102 SA-102 99.7 28.7 SAM-103 SA-103 104 37.2

From Table 4 it is clear that by immersing a glass slide for 10 minutesin an organic thin film forming solution, an organic thin film withexcellent water repellency and oil repellency can be formed rapidly.

(22) Organic Thin Film Formation-4

0.65 g of the metal-based surfactant M-1 and 1.3 g of a 3.5% by weighttoluene solution of titanium tetraisopropoxide were dissolved in 99 g ofhydrous toluene (water content: 460 ppm), and the solution was left toage for one day. 2.0 g of distilled water was then added to thissolution, and the resulting solution was left to stand for a further oneday, thus yielding an organic thin film forming solution (SA-104).Subsequently, glass slides were immersed for 5 minutes in the thusprepared organic thin film forming solution (SA-104), and these glassslides were then removed, the surfaces were washed with toluene, and theslides were dried for 10 minutes at 60° C., thereby yielding glassslides with an ODS organic thin film (SAM-104) formed on the surfacesthereof.

A microsyringe was used to drip 5 μl of water or tetradecane onto thesurface of sample of organic thin film-coated glass slides obtainedabove, and the slides were then left to stand for 60 seconds.Subsequently, the contact angle at the water and tetradecane dropsurface was measured using a contact angle measurement device (360S,manufactured by Enna Inc.). The results revealed a water contact angleof 106.3° and a tetradecane contact angle of 35.8°.

(23) Organic Thin Film Formation-5

0.65 g of the metal-based surfactant M-1 and 0.3 g of titanium oleate(manufactured by Mitsuwa Chemicals Co., Ltd.) were dissolved in 99 g ofhydrous toluene (water content: 460 ppm), and the solution was left toage for one day. 2.0 g of distilled water was then added to thissolution, and the resulting solution was left to stand for a farther oneday, thus yielding an organic thin film forming solution (SA-105).Subsequently, glass slides were immersed for 5 minutes in the thusprepared organic thin film forming solution (SA-105), and these glassslides were then removed, the surfaces were washed with toluene, and theslides were dried for 10 minutes at 60° C., thereby yielding glassslides with an ODS organic thin film (SAM-105) formed on the surfacesthereof.

A microsyringe was used to drip 5 μl of water or tetradecane onto thesurface of separate organic thin film-coated glass slides obtainedabove, and the slides were then left to stand for 60 seconds.Subsequently, the contact angle at the water and tetradecane dropsurface was measured using a contact angle measurement device (360S,manufactured by Erma Inc.). The results revealed a water contact angleof 103.5° and a tetradecane contact angle of 32.2°.

(24) Organic Thin Film Formation-6

(Preparation of Titanium Complex Solution)

To samples of hydrous toluene were added 1 g of a 3.5% by weight toluenesolution of titanium tetraisopropoxide, and the various coordinationcompounds shown in Table 5, thus yielding a series of titanium complexsolutions (T-1 to T-5). The quantity used of the hydrous toluene, andthe nature and quantity of each of the coordination compounds are shownin Table 5.

TABLE 5 Organic thin film forming solution Titanium complex QuantityHydrous solution Type added toluene T-1 trifluoroacetic acid 0.40 g 26.9g T-2 acetylacetone 0.35 g 26.9 g T-3 ethyl acetoacetate 0.46 g 26.8 gT-4 tetrahydroethane 0.25 g 27.0 g T-5 pyridine 0.28 g 27.0 g

(Organic Thin Film Formation, Organic Thin Film Evaluation)

0.65 g of the metal-based surfactant M-1, 13 g of a titanium complexsolution (T-1 to T-5), and 2.0 g of distilled water were added to 99 gsamples of water-saturated toluene (water content: 460 ppm), and theresulting solutions were left to age for one day, thus yielding organicthin film forming solutions (SA-106 to SA-110). Subsequently, glassslides were immersed for 5 minutes in the thus prepared organic thinfilm forming solutions (SA-106 to SA-110), and these glass slides werethen removed, the surfaces were washed with toluene, and the slides weredried for 10 minutes at 60° C., thereby yielding glass slides with anODS organic thin film (SAM-106 to SAM-110) formed on the surfacesthereof.

A microsyringe was used to drip 5 μl of water or tetradecane onto thesurface of sample of organic thin film-coated glass slides obtainedabove, and the slides were then left to stand for 60 seconds.Subsequently, the contact angle at the water and tetradecane dropsurfaces was measured using a contact angle measurement device (360S,manufactured by Erma Inc.). The results are shown in Table 6. In Table6, the units for the contact angles are degrees (°).

TABLE 6 Titanium Organic thin Organic thin film contact Organic complexfilm forming angle (°) thin film solution solution Water TetradecaneSAM-106 T-1 SA-106 97.4 26.6 SAM-107 T-2 SA-107 103.0 27.4 SAM-108 T-3SA-108 103.5 32.2 SAM-109 T-4 SA-109 105.8 35.5 SAM-110 T-5 SA-110 103.535.3

From Table 6 it is clear that by immersing glass slides for 10 minutesin the organic thin film forming solutions SA-106 to SA-110, organicthin films with excellent water repellency and oil repellency can beformed rapidly.

(25) Organic Thin Film Formation-7

(Preparation of Titanium Complex Solution)

0.51 g of an alkoxy titanium hydrolysis product (A-10, manufactured byNippon Soda Co., Ltd.) was added to 19.2 g of hydrous toluene, and 0.25g of acetylacetone (or 0.33 g of ethyl acetoacetate) was then added as acoordination compound, thus forming a titanium complex solution (T-6 orT-7).

(Organic Thin Film Formation, Organic Thin Film Evaluation)

0.65 g of the metal-based surfactant M-1, 1.3 g of the titanium complexsolution (T-6 or T-7), and 2.0 g of distilled water were added to 99 gsamples of hydrous toluene (water content: 460 ppm), and the resultingsolutions were left to age for one day, thus yielding organic thin filmforming solutions (SA-111 and SA-112) Subsequently, glass slides wereimmersed for 5 minutes in the thus prepared organic thin film formingsolutions (SA-111 and SA-112), and these glass slides were then removed,the surfaces were washed with toluene, and the slides were dried for 10minutes at 60° C., thereby yielding glass slides with an ODS organicthin film (SAM-111 and SAM-112) formed on the surfaces thereof.

A microsyringe was used to drip 5 μl of water or tetradecane onto thesurface of separate organic thin film-coated glass slides obtainedabove, and the slides were then left to stand for 60 seconds.Subsequently, the contact angle at the water and tetradecane dropsurfaces was measured using a contact angle measurement device (360S,manufactured by Erma Inc.). The results are shown in Table 7. In Table7, the units for the contact angles are degrees (°).

TABLE 7 Titanium Organic thin Organic thin film contact Organic complexfilm forming angle (°) thin film solution solution Water TetradecaneSAM-111 T-6 SA-111 101.2 34.8 SAM-112 T-7 SA-112 104.9 33.1

From Table 7 it is clear that by immersing glass slides for 10 minutesin the organic thin film forming solutions SA-111 and SA-112, organicthin films with excellent water repellency and oil repellency can beformed rapidly.

(26) Organic Thin Film Formation-8

(Preparation of Organic Thin Film Forming Solution)

To hydrous toluene with a water content of 350 ppm was added sufficientquantity of the metal-based surfactant M-1 to produce a final ODSconcentration of 0.5% by weight, and the resulting mixture was stirredfor 30 minutes at room temperature. To this solution was then addedsufficient quantity of a 1% by weight hydrous toluene solution oftetrakis(trimethylsiloxy)titanium (T-8) (manufactured by AZmax Co.,Ltd.) to produce a ratio (number of mols of ODS): (number of titaniumoxide-equivalent mols within (T-8)) of 98:2, and the resulting mixturewas then stirred for three hours at room temperature. A 100 g sample ofthe resulting reaction solution was transferred to a bottle with aninternal capacity of 1000 ml, and using an 18 liters/minute blower and aKinoshita glass ball filter, saturated water vapor was bubbled throughthe solution at 25° C., yielding an organic thin film fowling solution(SA-113) in which the moisture content had been adjusted to 510 ppm.

(Organic Thin Film Formation, Organic Thin Film Evaluation)

Alkali-free glass substrates (product number: AN100, manufactured byAsahi Glass Co., Ltd.) and silicon wafers (Si) that had been subjectedto ultrasound cleaning and ozone cleaning were immersed in the organicthin film forming solution obtained above for the immersion time periodsshown in Table 8, and were then removed from the solution. Thesubstrates were then subjected to ultrasound cleaning in toluene, andthen dried at 60° C. for 10 minutes, thereby forming substrates withorganic thin films formed on the surfaces thereof (SAM-113 (AN100) andSAM-114 (Si)).

Subsequently, a microsyringe was used to drip 5 μl of water orTetradecane onto the organic thin film on the surface of each of thesubstrates (AN100 and Si) obtained above, and the contact angle at theorganic thin film surface was measured using a contact angle measurementdevice (360S, manufactured by Erma Inc.). The results of themeasurements are shown in Table 8.

TABLE 8 Substrate with Immersion Organic thin film contact organic thinfilm time angle (°) formed thereon Substrate (minutes) Water TetradecaneSAM-113 AN-100 3 104 34 SAM-114 Si 5 105 33

In addition, the organic thin films formed on the surfaces of each ofthe substrates (AN100, Si) were then subjected to ultrasound cleaningfor one hour in water, and the contact angles were then remeasured. Forboth substrates (AN100, Si), no reduction in the contact angle wasobserved as a result of the ultrasound cleaning, confirming that in bothcases, an organic thin film with excellent adhesiveness had been formedon the substrate surface.

(27) Organic Thin Film Formation-9

(Preparation of Organic Thin Film Forming Solution)

To hydrous toluene with a water content of 350 ppm was added sufficientquantity of the metal-based surfactant M-1 to produce a final ODSconcentration of 0.5% by weight, and the resulting mixture was stirredfor 30 minutes at room temperature. To this solution was then addedsufficient quantity of a 1% by weight hydrous toluene solution ofbenzoic acid (T-9) to produce a ratio (number of mols of ODS): (numberof mols of benzoic acid within (T-9)) of 10:1, the resulting mixture wasstirred at room temperature, a 100 g sample of the reaction solution wastransferred to a bottle with an internal capacity of 1000 ml, and usingan 18 liters/minute blower and a Kinoshita glass ball filter, saturatedwater vapor was bubbled through the solution at 25° C., yielding anorganic thin film fowling solution (SA-114) in which the moisturecontent had been adjusted to 452 ppm.

With the exception of using either a 1% by weight hydrous toluenesolution of capric acid (T-10) or a 1% by weight hydrous toluenesolution of acetic acid (T-11) instead of the benzoic acid, the organicthin film forming solutions (SA-115 and SA-116) in which the moisturecontent had been adjusted to 317 ppm and 434 ppm respectively wereprepared in the same manner as described above.

(Organic Thin Film Formation, Organic Thin Film Evaluation)

Soda lime glass substrates (S-1126, manufactured by Matsunami GlassInd., Ltd.) that had been subjected to ultrasound cleaning and ozonecleaning were immersed in each of the organic thin film formingsolutions (SA-114 to SA-116) obtained above for 30 minutes, and werethen removed from the solution. The substrate surfaces were thensubjected to ultrasound cleaning in toluene, and then dried at 60° C.for 10 minutes, thereby forming substrates with organic thin filmsformed on the surfaces thereof.

A microsyringe was used to drip 5 μl of water or tetradecane onto thesurface of each of the substrates, and the substrates were then left tostand for 60 seconds. Subsequently, the contact angle at the water andtetradecane drop surface was measured using a contact angle measurementdevice (360S, manufactured by Erma Inc.). The results are shown in Table9. In Table 9, pKa refers to the value obtained by measuring the aciddissociation constant for an aqueous solution of the organic acid used.In Table 9, the units for the contact angles are degrees (°).

TABLE 9 Organic thin Organic thin film contact film forming Organic acidsolution angle (°) solution Type pKa Water Tetradecane SA-114 Benzoicacid (T-9) 4.20 104.6 32.1 SA-115 Capric acid (T-10) 4.89 114.4 25.3SA-116 Acetic acid (T-11) 4.56 83.8 19.6

From Table 9 it is clear that when an organic acid with a pKa of 1 to 6,and preferably from 2 to 5, is used, no reduction in the contact angleis observed as a result of the ultrasound cleaning, confirming that forboth substrates, an organic thin film with excellent adhesiveness isformed on the substrate surface.

(28) Organic Thin Film Formation-10

In a clean room under conditions including a temperature of 25° C. and ahumidity of either 30% RH or 80% RH, an ozone-cleaned, rectangular,alkali-free glass substrate of dimensions 2 cm×5 cm was immersed in 100g of the solution SA-2 (water content: 480 ppm), and this immersionprocess was repeated consecutively for 7 substrates, with an interval of10 minutes between immersion repetitions. For each repetition, thesubstrate was immersed for 3 minutes, removed from the solution,subjected to ultrasound cleaning in toluene, and then dried at 60° C.for 10 minutes, thereby forming an organic thin film. The results aresummarized in Table 10.

TABLE 10 Organic thin film contact angle: water (°) Immersion repetitionHumidity 30% RH Humidity 80% RH 1st repetition 104 105 4th repetition 86 104 7th repetition  77 105 Water content at 180 ppm 600 ppmcompletion

From Table 10 it is clear that in the environment at a humidity of 80%RH, thin films with a large contact angle of 100° or higher were able tobe produced with good reproducibility with short immersion times. Incontrast, in the environment at a humidity of 30% RH, the contact anglefell as the number of repetitions increased. From this finding it isclear that in a low humidity environment, the water content of theorganic thin film forming solution decreases during the immersionprocess, making it impossible to form dense monomolecular films.

(29) Monomolecular Film Formation

(Preparation of monomolecular film forming solution)

A monomolecular film forming solution was prepared using the catalystsolution and the metal-based surfactant described below.

The catalyst solution (C-2) prepared above in (2) CatalystPreparation-2. n-octadecyltrimethoxysilane (ODS: manufactured by GelestInc., referred to as metal-based surfactant M-1) as disclosed above in(8) Metal-based Surfactant-1.

Using the same method as that described above in (11) Organic Thin FilmForming Solution Preparation Method-2, the metal-based surfactant M-1was added to hydrous toluene with a water content of 350 ppm insufficient quantity to yield a final concentration of 0.5% by weight,and the mixture was then stirred at room temperature for 30 minutes.Subsequently, the catalyst C-2 was added dropwise to the solution in thepredetermined quantity shown in Table 11, and following completion ofthe dropwise addition, the mixture was stirred at room temperature forthree hours. A 100 g sample of the thus formed solution was transferredto a bottle, a glass fiber filter paper of diameter 3 cm (GA-100,manufactured by Toyo Rosin Co., Ltd.) that had been thoroughly wet withwater was immersed at the bottom of the bottle, and the bottle wassealed. The bottle was then allowed to stand at room temperature for twohours, yielding a monomolecular film forming solution (SA-201). Thewater content was 550 ppm. The results are summarized in Table 11. InTable 11, the water content prior to treatment represents the watercontent prior to adjustment of the water content of the monomolecularfilm forming solution.

The water content was measured using a Karl Fischer moisture meter(CA-07, manufactured by Dia Instruments Co., Ltd.) using a coulometrictitration method.

TABLE 11 Monomolecular Mixing Water content (ppm) film ratio* Watercontent Water content of forming Catalyst of M-1 prior to monomolecularfilm solution (C) and C treatment forming solution SA-201 C-2 90:10 350550 *The ratio of (number of mols of M-1):(metal oxide-equivalent numberof mols of metal component within C solution)

(Monomolecular Film Production Method-1)

A soda lime glass substrate (SLG), an alkali-free glass substrate(AN100, manufactured by Asahi Glass Co., Ltd.), and a silicon wafer (Si)that had been subjected to ultrasound cleaning and ozone cleaning wereeach sprayed with the monomolecular film forming solution (SA-201),using a low-pressure spray gun, until the entire substrate surface waswet. After a 10-second pause, the entire substrate surface was onceagain sprayed with the solution SA-201. During the first sprayapplication, the SA-201 solution exhibited favorable wettingcharacteristics across the entire substrate surface. During the secondspray application, the substrate surface appeared to repel the solutionSA-201. Following confirmation of this repellency, neat toluene solventwas sprayed from the same spray gun to wash the substrate surface.Subsequently, each of the substrates was dried at 60° C. for 10 minutes,yielding a monomolecular film (SAM-201 to 203).

(Monomolecular Film Production Method-2)

The monomolecular film forming solution (SA-201) prepared using themethod described above in (29) Monomolecular film formation-1 wasdripped onto a soda lime glass substrate (SLG), an alkali-free glasssubstrate (AN100, manufactured by Asahi Glass Co., Ltd.), and a siliconwafer (Si) that had been subjected to ultrasound cleaning and ozonecleaning, a polyester film was overlaid on top of each sample, and arubber roller was then rolled over the film surface, thereby spreadingthe monomolecular film forming solution (SA-201) uniformly and thinlybetween the substrate and the film. After being allowed to stand in thisstate for a predetermined period, the film was peeled off each sample,and the substrates were subjected to ultrasound cleaning in toluene andthen dried at 60° C. for 10 minutes, thus yielding monomolecular films(SAM-204 to 206).

(Monomolecular Film Evaluation)

Evaluation results (contact angle, film adhesiveness, XPS analysis) forthe monomolecular films, which were measured using the methods describedabove in (19) Evaluation of organic thin films, are summarized in Table12.

TABLE 12 Monomolecular film production Film properties MonomolecularFilm production Stand time Film contact angle (°) film method Substrate(minutes) Water Toluene Adhesiveness SAM-201 Production method-1 SLG —105 35 ∘ SAM-202 ″ AN100 — 106 36 ∘ SAM-203 ″ Si — 102 30 ∘ SAM-204Production method-2 SLG 1 106 36 ∘ SAM-205 ″ AN100 2 104 34 ∘ SAM-206 ″Si 5 105 32 ∘

From Table 12 it is clear that in the production method-1 and theproduction method-2, monomolecular films with favorable waterrepellency, oil repellency, and adhesiveness are being obtained withinshort time periods. Conventionally, it was thought that metal-basedsurfactants having hydrolyzable groups such as alkoxy groups and thelike could only be used to form monomolecular films by using dippingmethods, but by employing the method of the present invention, theformation of a monomolecular film on a large substrate using a smallquantity of solution is now possible. Confirmation of the production ofmonomolecular films was made by XPS analysis.

INDUSTRIAL APPLICABILITY

By using a method for producing an organic thin film according to thepresent invention, a dense self-assembly monomolecular film with minimalimpurities can be produced. Furthermore, a highly crystalline,monomolecular, and homogenous chemically adsorbed film with excellentadhesiveness can be formed even on an amorphous substrate.

A chemically adsorbed film of the present invention can be used in theformation of design patterns for electronic devices and the like, andcan also be extremely readily applied to devices requiring heatresistant, weather resistant, and abrasion resistant ultra-thincoatings, including electronic products, and particularly electronicappliances, vehicles, industrial equipment, mirrors, and optical lensesand the like, and as such, can be said to have a very high industrialvalue.

1. A method for producing an organic thin film in which an organic thinfilm is formed on a surface of a substrate, comprising a step (A) ofbringing said substrate into contact with an organic solvent solutioncomprising a metal-based surfactant having at least one hydrolyzablegroup, and a catalyst, wherein the water content within said organicsolvent solution is either set to or maintained within a range of from50 ppm to the saturated water content for the organic solvent, and saidcatalyst is at least one material selected from the group consisting oforganic acids and acid catalysts, wherein said organic solvent solutionis a hydrocarbon-based solvent solution or a fluorinatedhydrocarbon-based solvent solution.
 2. A method for producing an organicthin film according to claim 1, wherein said organic solvent solution isprepared by using from 0.001 to 1 mol, or an oxide-equivalent quantityof 0.001 to 1 mol, of said catalyst, per 1 mol of said metal-basedsurfactant.
 3. A method for producing an organic thin film according toclaim 1, wherein said water content within said organic solvent solutionis maintained within a range of from 50 ppm to the saturated watercontent for the organic solvent, and said step (A) is repeated at leasttwo times using the same solution.
 4. A method for producing an organicthin film according to claim 3, wherein in repeating said step (A) twoor more times, said step (A) is conducted with two or more substratesbeing brought into contact with the same solution.
 5. A method forproducing an organic thin film according to claim 1, wherein saidmetal-based surfactant having at least one hydrolyzable group is acompound represented by a formula (1) shown below:R¹ _(n)MX_(m−n)  (I) (wherein, R¹ represents a hydrocarbon group thatmay contain a substituent, a halogenated hydrocarbon group that maycontain a substituent, a hydrocarbon group containing a linkage group,or a halogenated hydrocarbon group containing a linkage group, Mrepresents at least one metal atom selected from a group consisting of asilicon atom, germanium atom, tin atom, titanium atom, and zirconiumatom, X represents a hydroxyl group or a hydrolyzable group, nrepresents an integer from 1 to (m−1), m represents an atomic valence ofsaid metal M, and in those cases where n is 2 or greater, said R¹ groupsare either identical or different, and in those cases where (m−n) is 2or greater, said X groups are either identical or different, although of(m−n) X groups, at least one X group is a hydrolyzable group).
 6. Amethod for producing an organic thin film according to claim 1, whereinsaid step of bringing said substrate into contact with said organicsolvent solution is conducted within a space that is maintained at ahumidity of at least 40% RH.
 7. A method for producing an organic thinfilm according to claim 1, wherein said step of bringing said substrateinto contact with said organic solvent solution is conducted within aspace that is maintained at a humidity of at least 60% RH.
 8. A methodfor producing an organic thin film according to claim 1, wherein saidorganic thin film is a crystalline organic thin film.
 9. A method forproducing an organic thin film according to claim 1, wherein saidorganic thin film is a monomolecular film.
 10. A method for producing anorganic thin film according to claim 3, wherein said metal-basedsurfactant having at least one hydrolyzable group is a compoundrepresented by a formula (1) shown below:R¹ _(n)MX_(m-n)  (I) (wherein, R¹ represents a hydrocarbon group thatmay contain a substituent, a halogenated hydrocarbon group that maycontain a substituent, a hydrocarbon group containing a linkage group,or a halogenated hydrocarbon group containing a linkage group, Mrepresents at least one metal atom selected from a group consisting of asilicon atom, germanium atom, tin atom, titanium atom, and zirconiumatom, X represents a hydroxyl group or a hydrolyzable group, nrepresents an integer from 1 to (m−1), m represents an atomic valence ofsaid metal M, and in those cases where n is 2 or greater, said R¹ groupsare either identical or different, and in those cases where (m−n) is 2or greater, said X groups are either identical or different, although of(m−n) X groups, at least one X group is a hydrolyzable group).
 11. Amethod for producing an organic thin film according to claim 3, whereinsaid step of bringing said substrate into contact with said organicsolvent solution is conducted within a space that is maintained at ahumidity of at least 40% RH.
 12. A method for producing an organic thinfilm according to claim 3, wherein said step of bringing said substrateinto contact with said organic solvent solution is conducted within aspace that is maintained at a humidity of at least 60% RH.
 13. A methodfor producing an organic thin film according to claim 3, wherein saidorganic thin film is a crystalline organic thin film.
 14. A method forproducing an organic thin film according to claim 3, wherein saidorganic thin film is a monomolecular film.
 15. A method for producing anorganic thin film in which an organic thin film is formed on a surfaceof a substrate, comprising a step (A) of bringing said substrate intocontact with an organic solvent solution comprising a metal-basedsurfactant having at least one hydrolyzable group, and a catalyst,wherein the water content within said organic solvent solution is eitherset to or maintained within a range from 50 to 1,000 ppm, and saidcatalyst is at least one material selected from the group consisting oforganic acids and acid catalysts, wherein said organic solvent solutionis a hydrocarbon-based solvent solution or a fluorinatedhydrocarbon-based solvent solution.
 16. A method for producing anorganic thin film in which an organic thin film is formed on a surfaceof a substrate, comprising a step (A) of bringing said substrate intocontact with an organic solvent solution comprising a metal-basedsurfactant having at least one hydrolyzable group, and a catalyst,wherein the water content within said organic solvent solution ismaintained within a range from 50 to 1,000 ppm, and said step (A) isrepeated at least two times using the same solution, and said catalystis at least one material selected from the group consisting of organicacids and acid catalysts, wherein said organic solvent solution is ahydrocarbon-based solvent solution or a fluorinated hydrocarbon-basedsolvent solution.